Gas Liquefaction

Thermodynamics
Chapter two
 Chapter objectives

Refrigeration
How can gases be
Liquefaction by cycles, their
converted to
refrigeration performance and
liquids?
refrigerants types

Liquefaction by Types of expansion

Innovative expansion (J-T liquefaction cycles
refrigeration cycles valve and and their
expanders) performance .
 • the gas to a
suitable
cooling temperature
Gases can
be
converted
to liquids • the gas to a
suitable pressure
by which is related to
compressing a certain
temperature for
each gas.
•Critical temperature: temperature
above which a gas cannot be
liquefied, regardless of the pressure
applied.
• Below the critical temperature, the
gas can be liquefied by pressure.
• Furthermore, the lower the
temperature below the critical
value, the lower the pressure
required for liquefaction
•Critical Pressure: Above the critical pressure,
increasing the temperature will not cause a fluid to
vaporize to give a two-phase system.(regasification)
•The critical pressure is also regarded as the vapor
pressure at the critical temperature.
•Critical State specifies the conditions (temperature,
pressure and sometimes composition) at which a
phase boundary ceases to exist.
•As the critical state is approached the properties of
the gas and liquid phases approach one another
resulting in only one phase at the critical point:
homogeneous supercritical fluid.
➢The table depicts that the state point of
methane at ambient conditions is a
superheated gas at this pressure and
temperature, existing at well above the
critical temperature but below the critical
pressure.
➢ Most gases existing in the atmosphere
are extremely superheated, but are at
pressures well below their critical
pressures.
➢Methane has a critical point at -82 ◦
C, and its liquefaction cannot be
done by compression alone.
➢ If the temperature and pressure of
a gas can be brought into the region
between the saturated liquid and
saturated vapor lines, then the gas
will become ‘wet’ and this ‘wetness’
will condense giving a liquid.
 If it is desired to liquefy a gas existing above its
critical temperature heat has to be taken out of the
gas (cooling). This can be done by two means:

Cooling the gas by

liquefy a gas existing above

heat transfer to a cold

its critical temperature

reservoir, i.e.
refrigeration;

J-T effect
Expanding the gas turboexpander
➢The first method requires a
heat sink at a temperature
lower than that to which the gas
is cooled and is commonly
used to precool a gas prior to
its liquefaction by the other
method.(technology)
Method (i) Liquefaction by cooling (refrigeration)

➢This method, in a single step, is satisfactory if

the liquefaction process does not require
very low temperatures.
➢ Several applications for refrigeration include
NGL recovery, LPG recovery,, and LNG plants.
➢A number of common gases can be obtained
in liquid form by cooling. Examples of these
are the hydrocarbons butane and propane,
which can both exist as liquids at room
temperature if they are contained at
moderately elevated pressures.(LPG)
Refrigeration cycle
•A refrigerator is a device used to
transfer heat from a low- to a high-
temperature medium. (reversed heat
engine.)
•The ideal refrigerator, works on a
reversed Carnot cycle.
•In this case the cycle consists of two
isothermal steps and two adiabatic
steps.
 The usual measure of the performance of a
refrigerator is called the coefficient of performance,
COP defined as:

 The coefficients of performance of Carnot

refrigerators is expressed in terms of temperatures
as follows;

 Noticethat COP increases as the difference between

the two temperatures decreases, that is, as TL rises
or TH falls. Besides, variation of TL has more
influence on the cycle COP than variation of TH
(COP) of a refrigerator can be greater than
1.0, i.e. the amount of heat removed from
the refrigerated space can be greater than
the amount of work input and normally
varies between 2 and 7
Thermodynamic analysis of Ideal VCRC
:Constant-temperature refrigeration cycle
•PH diagrams are more commonly used
in refrigeration work than TS diagrams
since they show directly the required
enthalpies;
•The refrigerant absorbs heat (QL ) from a
low-temperature medium (at T L ) in the
evaporator.
•Power (W) is added in a compressor to
compress the refrigerant to the condensing
pressure.
•The high-temperature refrigerant cools
into the liquid phase by rejecting the
heat (Q H ) to a high-temperature
medium (at T H ) in the condenser.
•The refrigerant in the liquid phase
enters the expansion valve and is
expanded to give a low temperature
and pressure two-phase mixture at the
evaporator inlet.
Fig (3) a, Vapor Compression Refrigeration Cycle using
(expansion valve)
Compression Step :
➢The power required and compressor discharge
temperature depends upon compressor efficiency
The work of compression is simply
Wact, c=(H3 -H2)/ƞ is
➢Where ƞ is is the adiabatic efficiency of the
compressor.
➢ Taking into account compressor nonideality, the
actual enthalpy at the end of the expansion is:
H3‾=H2+Wact,c
➢Compressor power to the refrigeration system is the
product of the mass flow rate and shaft work:
Power =m· × Wact,c
Condensation Step:
➢ The warm gas goes to an air- or water-
cooled condenser, where it cools and
totally condenses
➢ The condensing pressure of the
refrigerant is a function of the cooling
medium available air, cooling water, or
another refrigerant.
QH=H3‾ -H4
Expansion Step :
➢ The liquid flashes through an expansion valve,
where the temperature and pressure drop.
➢ No change occurs in the enthalpy, but the
temperature drops to the saturation temperature
of the liquid at the expansion-discharge
pressure, and
H1=H4 (isenthalpic process)
➢ In the throttling process the fluid flows through
a partly open valve without any appreciable
kinetic energy change and the result is a
pressure drop in the fluid
➢ The fraction, f, of refrigerant condensed is
computed knowing the initial enthalpy and
liquid and vapor enthalpies at the condensation
temperature, which for the given case is
Refrigeration Step:
➢ The cold refrigerant then goes to a heat
exchanger, the chiller, where it cools the
process stream by evaporation.
➢ The heat absorbed by the refrigerant
is simply
➢ QL=H2-H1
➢ Refrigeration-cycle performance is
calculated as:
COP=(H2-H1)/(H3‾ -H2)
➢the cycle in fig3 (b) is used in large installations
only. The process requires a turbine or expander that
operates on a two phase liquid/vapor mixture. Such
a machine is impractical for small units.
➢The fraction of refrigerant condensed and generated
work depend on the turbine efficiency
➢ Wact,t=(H4-H1)×ƞ is
➢Where ƞ is is the adiabatic efficiency of the
expander H1‾ =H4-Wact, t
➢In small units such as household refrigerators and air
conditioners the simplicity and lower cost of the valve
outweighs the energy savings possible with a
turbine.
Fig (3)b, Vapor Compression Refrigeration Cycle using
(turboexpander)
• Irreversible refrigeration cycle with finite
heat transfer temperature differences
• The ideal VCRC assumes zero temperature
difference between the refrigerant and
ambient/load at heat rejection and
absorption processes, respectively.
• However, such zero heat transfer
temperature difference requires an
infinitely large area of the heat exchanger,
which is impossible for practical
applications.
Q= UA∆Tlm
• In reality, in the heat rejection
process the temperature of the
refrigerant (TˉH ) is higher than the
ambient temperature (T H ), and in
the heat absorption process the
refrigerant temperature TˉL is lower
than the load temperature (TL).
• the reverse refrigeration cycle with
finite heat transfer temperature
difference is shown in Figure 4-5
❑QˉH and Q ˉL represent the heat rejection
and the cooling capacity in the
irreversible cycle, respectively. Thus,
according to the first law of
thermodynamics the internal reversible
cycle:
❑ The external irreversible cycle:

❑ Compared with the reversible Carnot cycle 1-2-3-

4-1, the coefficient of performance for the cycle
with heat transfer temperature difference is lower
than that with zero temperature difference; that is
If two cycles produce the same refrigeration
capacity:
❑ΔW can also be represented as the
shadow area difference within two
cycle lines. It has been found that:

❑additional work input for the irreversible

refrigeration cycle is equal to the
ambient temperature multiplied by the
entropy generation
Classification of refrigerants
In general, refrigerants are classified into two categories.
common
refrigerants
They are used in
refrigerators operating
as a closed loop. There is
no accumulation or
withdrawal of product in
a refrigerator.
they have relatively high
critical temperatures and can
be liquefied near ambient or
medium cold temperatures.
Propane, freons
cryogenic
fluids
Cryogenic fluids are used
in open liquefiers where
liquid products are
removed and equivalent
make-up stream must be
added.
They have very low
boiling temperatures,
usually below 120 K.
methane, oxygen,
nitrogen
• The most common light hydrocarbon
refrigerant cooling temperature ranges
are (evaporation temperature):
• Methane -200 to -300F (-129 to -184C)
• Ethylene and ethane -75 to -175F (-59
to -115C)
• Propylene and propane +40 to -50F
(4.4 to -46C)
The Choice of Refrigerant (common
refrigerants)
•Characteristics such as toxicity, flammability,
cost , corrosion properties and vapor
pressure in relation to temperature are of
great importance when choosing the refrigerant.
•The vapor pressure of the refrigerant at the
evaporator temperature should be greater than
atmospheric pressure preventing the air
infiltrating into the low pressure components
 The vapor pressure of the refrigerant at the
condenser temperature should not be
unreasonably high, because of the high initial
cost and operating expenses of high-pressure
equipment.
 The volumetric refrigerating capacity is high,
which will reduce the size of the compressor
and refrigerant flow rate.
 Note volumetric refrigerating capacity is
defined as the cooling capacity per unit
volume of the vapor refrigerant at the outlet of
the evaporator .
 Typical
refrigerants are inorganic
compounds, halocarbon compounds, and
hydrocarbons.
Table 3.2 shows that only propane can be
liquefied by heat exchange with cooling water
at moderately high pressure.
All lower boiling gases require refrigeration by
means of a refrigerant prior to a final
compression step which results in liquefaction.
 How can NG be liquefied by cooling using
refrigeration cycle?
LNG at -
NG at 25 161 ᵒC
ᵒC

Evaporator
Refrigerant
mixed phase Refrigerant
saturated
vapors
To liquefy a boiling gas, it has to be cooled below its
dew point (the temperature at which condensation
starts taking place at a given pressure).
Innovative VCR systems:(cascade
refrigeration and mixed refrigerant)
➢ Main principle :To achieve the extremely cold or
cryogenic temperatures required to produce
LNG, work must be put into the refrigerant
cycle(s) through a refrigerant compressor(s),
and heat must be rejected from the cycle(s)
through air or water coolers.
➢ The primary objectives : of these technological
innovations are to increase the volume of LNG
production and optimize the efficiency of the
refrigeration process employed.
➢The maximum thermodynamic efficiency in
a liquefaction cycle is realized when the
heating curve of the refrigerant corresponds
to the cooling curve of the natural gas being
liquefied. (technology)
➢ This relation means that both ∆T (and thus
∆S) are zero for the heat transfer process.
These principles result in a more efficient
thermodynamic process, requiring less
power per unit of LNG produced, and
they apply to all liquefaction processes.
Gas liquefaction process - ideal
Example: Natural gas at 60 bar, 10o C ambient temperature
Ideal work of liquefaction: Natural gas at 60 bar: 0.11 kWh/kg
(0.8 % of Lower Heating Value)
➢ Observing the cooling curve of a typical natural
gas liquefaction process, three zones can be
noted in the process of the gas being liquefied. A
precooling zone, followed by a liquefaction
zone, and completed by a subcooling zone.
➢ All of these zones are characterized by having
different curve slopes, or specific heats, along
the process.
➢ Figure (4)is a schematic of a cooling curve for a
natural gas system and heating curves for a
mixed refrigerant system and a three-fluid
cascade system.
Fig.4, Typical Natural Gas/Refrigerant cooling curves
➢The area between the LNG cooling curve (orange line
above) and the refrigeration heating curve (green line below)
represents the amount of heat lost during the liquefaction
process.
➢The area above the refrigeration line represents the
amount of work done by the system and the closer the lines
are to each other the less work the system has to do.
➢The natural gas and mixed refrigerant curves show marked
curvature because the fluids are mixtures.
➢Thermodynamically, the mixed refrigerant comes closest to
a reversible process because it minimizes the temperature
difference between the two fluids.
➢Because both types of cycles are in use for LNG production,
we discuss the more important features of both processes.
• Cascade Refrigeration
• Concept it attempts to approximate the cooling curve
and reduces the irreversible heat exchange losses by use
of a series of refrigerants (usually three) in separate
loops whose refrigerants vaporize at different but constant
temperatures, that is a function of the saturation pressure.
• The cascade process starts with a vapor that can be
liquefied at ambient temperature by the application of
pressure only. The liquid formed by pressurization is then
expanded to a lower pressure, which results in a partial
vaporization and cooling of the remaining liquid.
• This cold liquid is then used to cool a second gas so that
it may also be liquefied by the application of moderate
pressure and then expanded to a lower pressure.
• The temperature reached in the expansion of the second liquid
will be substantially lower than that achieved by the expansion of
the first liquid.
• The third refrigerant on expansion reach very low temperature
lower than the required final temp. of the LNG.
• In principle, any number of different fluids may be used and
any desired temperature level can be reached by use of the
appropriate number of expansion stages.
• In practice, however, three fluid and three levels of expansion
are normal.
• The liquefaction of natural gas is achieved by means of a
ternary cascade refrigeration cycle, and the components are
shown in Fig (5).
• In the liquefaction of natural gas, the custom now is to use a
propane-ethylene (or ethane)-methane cascade fig(5).
Fig.(5), Plant for liquefaction of natural gas using closed
cascade process
• Mixed-Refrigerant
• Concept :(MR) cycle involves the continuous cooling of a
natural gas stream using a carefully selected blend of
refrigerants that can mimic the cooling curve of natural gas
from ambient to cryogenic temperatures.
• Mixed refrigerant cycles, on the other hand, do not maintain
a constant evaporating temperature at a given pressure. Their
evaporating temperature range, called temperature glide, is
a function of their pressure and composition.
• Typical refrigerant mixtures are a mixture of three or more
of hydrocarbons (like methane or ethane) and nitrogen.
• Finding optimal mass fractions of constituents of refrigerant
mixtures, which have the closest match between the cooling
and heating curves, would require optimizing several
variables (e.g., component mass fractions and pressure
levels)..
➢The MR cycles possess several advantages over the
classical cascade system.
➢The principal advantage is the use of a single
compressor refrigerant system in place of the three
refrigerant compressors and cycles of the standard
cascade.
➢Ability to adjust refrigerant compositions to
accommodate the changes in gas composition, feed
gas throughput, and plant operating pressure.,
➢The disadvantage when compared with the standard
cascade is the necessity for having facilities to
recover, store, and blend the components in the
refrigerant cycle.
Types of MR cycles: Actual cycles that used mixed
refrigerants appear in a variety of configurations, but
they can be loosely grouped into two basic categories

closed open
cycles cycles.
➢Almost all of the industrial processes in
current use are “cold box” processes in which
the process stream is cooled by a series of
refrigerants, either pure or mixed.
➢A major goal of these processes is to bring the
temperature approaches to an optimum value
in the heat exchangers, to lower the rate of
entropy creation, and thus lost work.
• Closed cycles
• The refrigerant mixture is compressed and then
partially condensed in a water-cooled exchanger.
• The refrigerant then undergoes a series of pressure
reductions and liquid-vapor separations to provide
the cold fluid needed in the heat exchangers to
liquefy the natural gas.
• The temperatures attained in the various heat
exchangers depend on the composition of the
refrigerant and the pressure to which the gas is
initially compressed.
• In this cycle, the natural gas passes through all four
heat exchangers in series and is then expanded into
a separator, where the liquid and vapor fractions are
separated.
• Open Cycle
• The natural gas stream to be liquefied is physically mixed
with the refrigeration cycle stream.
• After compression, the united gas streams are partially
condensed in a water-cooled. or air-cooled heat exchanger,
and then separated into liquid and vapor fractions in a
separator. From this point, the process is similar to the
closed cycle system.
• The vapor from the last separator is condensed in the final
heat exchanger, and then expanded and separated into an
LNG product and a flash gas that would generally be used
for plant fuel.
• To prevent heavy hydrocarbons from plugging in the
low-temperature portion of the cycle a liquid slipstream
may be withdrawn at a relatively high temperature.