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Liquefaction of Gases
Liquefied natural gas (LNG)
• Liquefied natural gas (LNG) is natural gas (predominantly methane, CH4,
with some mixture of ethane C2H6) that has been converted to liquid form
for ease and safety of non-pressurized storage or transport.
• It takes up about 1/600th the volume of natural gas in the gaseous state
(at standard conditions for temperature and pressure).
• It is odorless, colorless, non-toxic and non-corrosive. Hazards include
flammability after vaporization into a gaseous state, freezing and asphyxia
(oksijensizlikten boğulma).
• The liquefaction process involves removal of certain components, such as
dust, acid gases, helium, water, and heavy hydrocarbons, which could
cause difficulty downstream.
• The natural gas is then condensed into a liquid at close to atmospheric
pressure by cooling it to approximately −162 °C; maximum transport
pressure is set at around 25 kPa (effective).
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Liquefied natural gas (LNG)
• A typical LNG process. The gas is first extracted and transported to a
processing plant where it is purified by removing any condensates
such as water, oil, mud, as well as other gases such as CO2 and H2S.
• An LNG process train will also typically be designed to remove trace
amounts of mercury from the gas stream to prevent mercury
amalgamating with aluminium in the cryogenic heat exchangers.
• The gas is then cooled down in stages until it is liquefied. LNG is
finally stored in storage tanks and can be loaded and shipped.
Liquefied natural gas (LNG)
• Natural gas is mainly converted into LNG to achieve the natural gas transport
over the seas where laying pipelines is not feasible technically and
economically.
• LNG achieves a higher reduction in volume than compressed natural gas
(CNG) so that the (volumetric) energy density of LNG is 2.4 times greater than
that of CNG (at 250 bar) or 60 percent that of diesel fuel.
• This makes LNG cost efficient in marine transport over long distances.
• However, CNG carrier can be used economically up to medium distances in
marine transport.
• Specially designed cryogenic sea vessels (LNG carriers) or cryogenic road
tankers are used for its transport.
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Liquefied natural gas (LNG)
• LNG is principally used for transporting natural gas to markets, where
it is regasified and distributed as pipeline natural gas.
• It can be used in natural gas vehicles, although it is more common to
design vehicles to use compressed natural gas. Its relatively high cost
of production and the need to store it in expensive cryogenic tanks
have hindered widespread commercial use.
• Despite these drawbacks, on energy basis LNG production is expected
to hit 10% of the global crude production by 2020.
Liquefied natural gas (LNG)
Liquid density Saturation Pressure Saturation Temperature
(for boiling point) (for boiling point)
422.5 kg/m3 101.3 kPa -161.7 oC
385.8 kg/m3 490.7 kPa -138.2 oC
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Three-Stage (Ternary) Cascade
Refrigeration Systems
Boiling points of Propane (C3H8)
Pressure Temperature
1 atm -42.1 oC
10.8 bar 30 oC
Boiling points of Ethane (C2H6)
Pressure Temperature
1 atm -88.7 oC
9.7 bar -33.2 oC
Boiling points of Methane (CH4)
Pressure Temperature
1 atm -161.7 oC
46 atm -83.2 oC
Ref: Ibrahim Dinçer and Mehmet Kanoglu,
Refrigeration Systems and Applications, Second Edition, 2010 John Wiley & Sons.
Propane (C3H8)
Propane is a three-carbon alkane with the molecular formula C3H8. It is a gas at
standard temperature and pressure, but compressible to a transportable
liquid. A by-product of natural gas processing and petroleum refining, it is
commonly used as a fuel. Propane is one of a group of liquefied petroleum
gases (LP gases). The others include butane, propylene, butadiene, butylene,
isobutylene, and mixtures thereof.
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Ethane (C2H6)
Ethane is an organic chemical compound with chemical formula C2H6. At
standard temperature and pressure, ethane is a colorless, odorless gas. Like
many hydrocarbons, ethane is isolated on an industrial scale from natural gas
and as a petrochemical by product of petroleum refining. Its chief use is as
feedstock for ethylene production.
Three-Stage (Ternary) Cascade Refrigeration Systems
Cascade refrigeration cycles are commonly used in the liquefaction of natural gas,
which consists basically of hydrocarbons of the paraffin series, of which methane
has the lowest boiling point at atmospheric pressure.
Refrigeration down to that temperature can be provided by a ternary cascade
refrigeration cycle using propane, ethane, and methane, whose boiling points at
standard atmospheric pressure are 231.1 K (-42.1 C), 184.5 K (-88.7 C), and 111.7 K
(-161.5 C), respectively.
In the operation, the compressed methane vapor is first cooled by heat exchange
with the propane in the propane evaporator before being condensed by heat
exchange with the ethane in the ethane evaporator, thus reducing the degree of
irreversibility involved in the cooling and condensation of the methane.
Also, because of the high temperature after compression, the gas leaving each
compressor passes first through a water-cooled intercooler. In a large-scale plant of
this type, the compressors become rotary turbomachines instead of the
reciprocating types.
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Liquefaction of Gases
• Cryogenics is associated with low temperatures, usually defined to be below -100 ◦C (173 K).
• The general scope of cryogenic engineering is the design, development, and improvement of low-temperature
systems and components.
• The applications of cryogenic engineering include;
liquefaction of gases,
separation of gases,
high-field magnets,
sophisticated electronic devices that use the superconductivity property of materials at low temperatures,
space simulations,
food freezing,
medical procedures such as cryogenic surgery,
and
various chemical processes
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Liquefaction of Gases
• The liquefaction of gases has always been an important area of refrigeration since many
important scientific and engineering processes at cryogenic temperatures depend on
liquefied gases.
• Some examples of such processes are;
the separation of oxygen and nitrogen from air,
preparation of liquid propellants for rockets,
study of material properties at low temperatures,
and
study of some exciting phenomena such as superconductivity.
• At temperatures above the critical-point, a substance exists in the gas phase only. The
critical temperatures of helium, hydrogen, and nitrogen (three commonly used liquefied
gases) are -268, -240, and -196 ◦C, respectively.
• Therefore, none of these substances will exist in liquid form at atmospheric conditions.
Furthermore, low temperatures of this magnitude cannot be obtained with ordinary
refrigeration techniques.
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Linde–Hampson Cycle
• Makeup gas is mixed with the uncondensed portion of the gas from the previous cycle, and the mixture at state 2 is compressed by a
multistage compressor to state 3.
• The compression process approaches an isothermal process due to intercooling. The high-pressure gas is cooled in an aftercooler by a
cooling medium or by a separate external refrigeration system to state 4.
• The gas is further cooled in a regenerative counter-flow heat exchanger by the uncondensed portion of gas from the previous cycle to
state 5, and it is throttled to state 6, which is a saturated liquid–vapor mixture state.
• The liquid (state 7) is collected as the desired product, and the vapor (state 8) is routed through the regenerator to cool the high-
pressure gas approaching the throttling valve.
• Finally, the gas is mixed with fresh makeup gas, and the cycle is repeated.
Liquefaction of Gases
Multistage compression
with intercooling
Linde-Hampson system for liquefying gases.
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Linde–Hampson Cycle
• Several cycles, some complex and others simple, are used successfully for the
liquefaction of gases.
• Makeup gas is mixed with the uncondensed
portion of the gas from the previous cycle, and the
mixture at state 1 is compressed by
an isothermal
compressor to state 2.
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Linde–Hampson Cycle
• The temperature is kept constant by rejecting compression heat to a coolant by
multi-stage compression.
• The high-pressure gas is further cooled in a regenerative counter-flow heat
exchanger by the uncondensed portion of the gas from the previous cycle to state 3,
and is then throttled to state 4, where it is a saturated liquid–vapor mixture.
• The vapour (state 5) is routed through the heat exchanger and the liquid
(state 6) is collected as the desired product, to cool the
high-pressure gas approaching the throttling valve.
• Finally, the gas is mixed with fresh makeup gas, and the
cycle is repeated.
• The refrigeration effect for this cycle can be defined as
the heat removed from the makeup gas in order to turn
it into a liquid at state 6.
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Linde–Hampson Cycle
• Assuming ideal operation for the heat exchanger (i.e., the gas leaving the heat
exchanger and the makeup gas are at the same state as state 1, which is the
compressor inlet state; this is also the dead state: T1 = T0)
• The refrigeration effect per unit mass of the liquefied gas is given by
hf : the enthalpy of saturated liquid that is withdrawn
• From an energy balance on the cycle, the refrigeration
effect per unit mass of the gas in the cycle prior to
liquefaction may be expressed as
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Linde–Hampson Cycle
• Maximum liquefaction occurs when the difference between h1 and h2 (i.e., the
refrigeration effect) is maximized.
• The fraction of the gas in the cycle that is liquefied.
• An energy balance on the heat exchanger gives
where x is the quality of the mixture at state 4.
• The fraction of the gas that is liquefied may also be
determined from
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Linde–Hampson Cycle
• An energy balance on the compressor gives the work of compression per unit
mass of the gas in the cycle as
• Note that T1 = T0. The last term in this equation is the isothermal heat rejection
from the gas as it is compressed.
• The COP of this cycle is given by
• In liquefaction cycles, a performance parameter used
is the work consumed in the cycle for the liquefaction of
a unit mass of the gas.
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Example: An illustrative example for the simple
Linde–Hampson cycle
Assumptions:
• the compressor is reversible and isothermal
• the heat exchanger has an effectiveness of 100%
(i.e., the gas leaving the liquid reservoir is heated in the
heat exchanger to the temperature of the gas leaving the
compressor)
• the expansion valve is adiabatic
• no heat leak to the cycle
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Example: An illustrative example for the simple Linde–Hampson cycle
• The gas is taken to be air at 25 ◦C and 1 atm (0.101 MPa) at the compressor
inlet.
• The pressure of the gas is 20 MPa at the compressor outlet.
• The COP of a Carnot refrigerator is expressed by the temperatures of the heat
reservoirs
• Here, T represents the temperature of the gas being
liquefied, which changes between T1 and T6 during the
liquefaction process.
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Example: An illustrative example for the simple
Linde–Hampson cycle
An average value of T may be obtained
with COPrev = 0.578 and T0 = 298.2 K (25 C), yielding T = 117.2 K (-156 C).
This is the temperature a heat reservoir would have if a
Carnot refrigerator with a COP of 0.578 operated between
this reservoir at 117.2 K and another reservoir at 25 ◦C.
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Example: An illustrative example for the simple
Linde–Hampson cycle
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Example: An illustrative example for the simple
Linde–Hampson cycle
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Example: An illustrative example for the simple
Linde–Hampson cycle
The liquefied mass fraction y and the actual work input versus
liquefaction temperature for oxygen
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Example: An illustrative example for the simple Linde–Hampson cycle
The actual and reversible COPs versus liquefaction temperature
for oxygen
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Example: An illustrative example for the simple Linde–Hampson cycle
The exergy efficiency and reversible work versus liquefaction
temperature for oxygen
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Example: An illustrative example for the simple Linde–Hampson cycle
The exergy efficiency versus liquefaction temperature for
various gases
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Example: An illustrative example for the simple Linde–Hampson cycle
The liquefied mass fraction y and the actual work input versus
gas inlet temperature for oxygen
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Example: An illustrative example for the simple Linde–Hampson cycle
The actual and reversible COPs versus gas inlet temperature for
oxygen
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Example: An illustrative example for the simple Linde–Hampson cycle
The exergy efficiency and reversible work versus gas inlet
temperature for oxygen
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Example: An illustrative example for the simple Linde–Hampson cycle
The exergy efficiency versus gas inlet temperature for various
gases
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Example: An illustrative example for the simple
Linde–Hampson cycle - Outcomes
As the liquefaction temperature increases and the inlet gas temperature
decreases
• the liquefied mass fraction, the actual COP, and the exergy efficiency increase,
• while actual and reversible work consumptions decrease
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RE-LIQUEFACTION AND REGASIFICATION
OF NATURAL GAS ON BOARD
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The critical point is the
point above which the gas
cannot be liquefied by
pressure alone.
Thus, above -82 °C, methane
cannot be liquefied – it
cannot be liquefied at 25 °C.
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The Need for Re-liquefaction off Boil Off Gas
• Boil-off is the formation of vapour by the ingress of heat through the cargo
containment system and into the liquid cargo.
• The design daily boil-off rate has dropped considerably since the early days of
liquefied gas shipping rates, which were more than 0.25%, compared to the
current industry standard rate of 0.15% per day for most LNG ships, and rates
as low as 0.10% now specified for the larger LNG ships.
Heat ingress to the liquid cargo through the containment system
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Membrane type LNG tank
Moss spherical
containment system
For membrane LNG ships, the insulation is either of
plywood boxes filled with perlite or polyurethane foam and
the thickness can be between 530 mm and 270 mm,
respectively.
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Liquefied Petroleum Gas (LPG) Re-liquefaction
Pressure-Enthalpy Diagram for
Propane
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Liquefied Petroleum Gas (LPG) Re-liquefaction
• Smaller LPG ships, less than 5,OOO m3, are normally fully pressurized Type C gas carriers and therefore do not
need to have a re-liquefaction system.
• For LPG, the lowest typical carriage temperature is that of propane a -42 oC.
Fully pressurized gas carriers
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Liquefied Petroleum Gas (LPG) Re-liquefaction
Cargo vapour is drawn from
the tanks to one or more of
the re-liquefaction plants. A
typical modern plant
comprises a liquid knock-out
drum; a two-stage
reciprocating compressor; a
sea water cooled condenser;
and an intercooler.
Re-liquefaction plant - Direct condensation of boil-off (two stage)
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Liquefied Petroleum Gas (LPG) Re-liquefaction
A cargo of butane on the
North sea in winter will
require very little plant
operation to keep it cold
since the boiling point of
butane is only -O.5°C
whereas a cargo of propane
(-42°C) in the Persian gulf will
require all plants operating at
full capacity to control cargo
tank pressures.
Re-liquefaction plant - Direct condensation of boil-off (two stage)
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LNG Re-liquefaction
• LNG is carried at it's atmospheric boiling temperature of about -160 oC.
• On-board LNG re-liquefaction plants have evolved from the shore side equivalents and use
the preferred closed 'Brayton Cycle', with nitrogen as the refrigerant and the final stage of
the system installed inside a
'cold box'.
• There are several different
designs of re-liquefaction systems
that could be used to re-liquefy
LNG boil-off vapour. However, only
the nitrogen systems are
considered for shipboard use.
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LNG Re-liquefaction
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LNG Re-liquefaction
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LNG Re-liquefaction
• The nitrogen from the turbo expander circulates through the cargo condenser, thus removing
the heat from the circulating LNG vapour, and allows the LNG to be returned to the cargo
tanks as a liquid.
• The expander and the cargo condenser must be instalIed inside an insulated 'cold box ', or
fixed refrigerated structure. This structure may follow one of two designs:
1) Structure filled with insulation such as perlite
with the temperature inside maintained by
the equipment located within it. Access
would require the removal of the insulation
and would be restricted to dry-docking.
2) An enclosure fabricated from insulating
panels, with the internal temperature
maintained by evaporators. This would allow
access for checking and maintenance of the
machinery to be undertaken on a periodic
basis.
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LNG Re-liquefaction
• Plant capacity: The amount of nitrogen in the cargo has a major effect on the re-liquefaction
plant’s capacity. If an LNG cargo was loaded in which the nitrogen content was 1%, this would
result in the boil-off vapor having a composition of approximately 80% methane and 20%
nitrogen by volume.
• The electrical demand capacity wiII be significant and an installed power of 5-6 MW will be
required just for the re-liquefaction plant.
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LNG Re-liquefaction
• As alternative propulsion methods were considered for LNG ships. The boil-off gas had to be
effectively dealt with at all times.
• The Gas Combustion Unit (GCU) was subsequently designed and will in most cases be on
board as a backup to the primary means, whether that is a re-liquefaction plant or to a dual
fuel propulsion system.
• The scale of the unit should not be underestimated - a large
quantity of 'dilution air' is added to cool the gas below 525°C.
This is the maximum exhaust temperature since the auto
ignition temperature of methane is 585°C.
It is simply a means
of taking the boil-off
gas and burning it in
a furnace, with the
products of
combustion being
released to
atmosphere.
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Re-gasification
What is re-gasification? One definition is the controlled vaporisation of a liquid (LNG) at a
constant pressure by increasing its temperature due to the addition of an external heat source.
• Large quantities of hot flue gas to flow into the sparge pipes header and sparge tubes. This
forms large quantities of small bubbles that enter and flow up through the internal heat
exchanger.
• Since one of the by-products of combustion is
water in the form of steam, this is condensed as
the bubbles flow up through the heat exchanger.
Its latent heat of vaporization as well as the
sensible heat is released to the tube bundle and
water is circulated through the heat exchange.
Type I - Submerged Combustion Vaporiser (SCV)
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Re-gasification
• The ORV type is where water is used as the heating medium and heat transferred to the LNG
through a rack of horizontal pipes containing LNG.
• This design has been prohibited in some locations because the drop in sea water
temperature as it passes through the vaporiser may damage fish egg stocks.
Type II - Open Rack Vaporiser (ORV)
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Re-gasification
The shell and tube uses steam and glycol/water heat exchangers to transfer heat to the LNG.
Type III - Shell and Tube Vaporiser
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Floating Storage and Regasification Units (FSRUs)
• Floating Storage and Regasification Units (FSRUs) are multi-function vessels, which combine
LNG storage and built-in regasification systems onboard a ship or barge.
• FSRUs can receive LNG directly from conventional and large LNG ships, storing it in insulated
tanks – and can regasify, or convert the LNG back into natural gas when needed.
• An FSRU typically costs under US$300 million to build and can offer a lower-cost, faster, more
flexible option. They can bring the benefits of LNG and natural gas quickly to where they are
needed most.
• Regasified LNG from the FSRU can flow into the local grid or be transported by pipeline. The
FSRU can also be used to create a regional LNG hub.
• The FSRU receives LNG from long-haul LNG ships
and then reloads LNG onto smaller LNG ships that
can access tighter ports or locations that may be
out of reach of the gas pipeline network.
• The FSRU can also replenish smaller bunkering
vessels to fuel LNG-powered ships passing through
the area. Ref: ExxonMobil
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Ertuğrul Gazi FSRU (Floating Storage & Gasification Unit)
BOTAŞ’ın büyük yatırımlarından biri olan ve Türk Denizcilik Sicili’ne kayıtlı ilk FSRU (Yüzer LNG
Depolama ve Gazlaştırma) gemisi olan Ertuğrul Gazi, 3 Nisan 2021 tarihinde Uluslararası Gemi
Sicili'ne kaydedilerek gemiye Türk bayrağı çekildi.
* Ref: https://www.botas.gov.tr/Sayfa/dortyol-fsru-terminali/699#gallery-2
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Ertuğrul Gazi FSRU (Floating Storage & Gasification Unit)
• 295 metre gemi boyu, 46 metre gemi genişliği ve 12,5 metre gemi draftı bulunan Ertuğrul
Gazi FSRU gemisinin 110 milyon Sm3 doğal gaza eşdeğer olan 170 bin m3 LNG depolama ve
günlük 28 milyon Sm3 gazlaştırma kapasitesi özelliği bulunmaktadır.
• FSRU sistemi yüksek basınçlı sisteme sahip olduğundan ilave bir kompresör istasyonuna
ihtiyaç duymamaktadır.
• Gazlaştırma operasyonunda deniz suyu yerine, "Glycol Water" kullanmaktadır. Deniz suyuyla
temas etmeden bütün operasyonu kendi teknolojisiyle yürütmektedir.
* Ref: https://www.botas.gov.tr/Sayfa/dortyol-fsru-terminali/699#gallery-2
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Utilizing LNG cold energy for power generation
rather than solely for regasification
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Marmara Ereğlisi BOTAŞ
LNG Terminal
https://www.botas.gov.tr/Sayfa/marmara-ereglisi-
lng-terminali/20
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Marmara Ereğlisi BOTAŞ LNG Terminali – LNG sevkiyatı
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Utilization of LNG cold energy
Adopting the Rankine Power Cycle at the LNG terminal, propane as the working fluid *
* Ref: Ersoy. H. K., Demirpolat. S.O. 2007. LNG’nin kriyojenik enerjisini kullanarak güç üretiminin araştırılması. ICCI
Bildiriler Kitabı, 235.
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References
• https://en.wikipedia.org/wiki/Liquefied_natural_gas
• Ibrahim Dinçer and Mehmet Kanoglu, Refrigeration Systems and
Applications, Second Edition, 2010 John Wiley & Sons.
• Çengel, Y. A., & Boles, M. A. (2001). Thermodynamics: An engineering
approach. Boston: McGraw-Hill.
• Re-liquefaction, gas combination units and re-gasification, Liquefied
Gas Ship Survey Course
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