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Chapter 15

Exergy Analysis of Cryogenic and


Liquefaction Systems
Chapter Outline
15.1 Introduction 319 15.4.1 System Description 329
15.2 Energy and Exergy Analyses of Gas Liquefaction 15.4.2 Analysis 329
Systems 320 15.4.2.1 TEACS 329
15.3 Exergy Analysis of a Multistage Cascade Refrigeration 15.4.2.2 Binary Power Plant 330
Cycle for Natural Gas Liquefaction 322 15.4.2.3 LH Liquefaction Cycle 331
15.3.1 Background 323 15.4.2.4 Utilization Factors 331
15.3.2 Description of the Cycle 323 15.4.3 Performance 331
15.3.3 Exergy Analysis 323 15.4.3.1 Performance Variations with
15.3.3.1 Evaporators and Condensers 324 Geothermal Mass Flow Rate 332
15.3.3.2 Overall Cycle 326 15.4.3.2 Performance Variations with
15.3.4 Minimum Work for the Liquefaction Process 326 Geothermal Source Temperature 333
15.3.5 Discussion 328 15.4.4 Further Discussion and Findings 333
15.4 Exergy Analysis of an Integrated Hydrogen Liquefaction 15.5 Closing Remarks 334
Using Geothermal Energy 328 Problems 334

engineering is the design, development, and improvement


ABSTRACT
In this chapter, the application of energy and exergy analyses
of low-temperature systems and components. Applications
to cryogenic and liquefaction systems is described. Cryogenic of cryogenic engineering include liquefaction and separa-
engineering is the design, development, and improvement of low- tion of gases, high-field magnets, and sophisticated elec-
temperature (usually below 150 C or 123 K) systems and tronic devices that use the superconductivity of materials at
components. Applications of cryogenic engineering include lique- low temperatures, space simulation, food freezing, medical
faction and separation of gases, high-field magnets and sophisti- uses such as cryogenic surgery, and various chemical
cated electronic devices that use the superconductivity of materials processes (ASHRAE Refrigeration, 2006).
at low temperatures, space simulation, food freezing, medical uses Progress in the production of cryogenic temperatures is
such as cryogenic surgery, and various chemical processes. A based to a great extent on advances in thermodynamics. A
comprehensive exergy analysis is presented of a multistage cascade solid understanding of the thermal processes within a refrig-
refrigeration cycle used for natural gas liquefaction, which is
eration cycle is not possible without a sound knowledge of
a cryogenic process. The multistage cascade cryogenic system is
described and an exergy analysis of the cycle components and the
the laws of thermodynamics and cyclic processes. During the
minimum work required for liquefaction are provided. early years of classical thermodynamics, between 1842 and
1852, Julius Robert Mayer, James Prescott Joule, Rudolf
KEYWORDS Clausius, William Thomson, and Hermann von Helmholtz
Exergy; Cryogenics; Liquefaction; Gas liquefaction; Cascade published important findings concerning the First and
refrigeration; Natural gas liquefaction; Hydrogen liquefaction;
Second Laws of Thermodynamics. Before that time, the
Efficiency.
main approaches involved trial and error and many experi-
ments. Even after, necessary data were often missing and
only became available much later (Foerg, 2002).
15.1 INTRODUCTION
The liquefaction of gases has always been an important
Cryogenics is associated with low temperatures, usually area of refrigeration since many important scientific and
below 150 C (123 K). The general scope of cryogenic engineering processes at cryogenic temperatures depend on

Exergy. http://dx.doi.org/10.1016/B978-0-08-097089-9.00015-2
2013 Ibrahim Dincer and Marc A. Rosen. Published by Elsevier Ltd. All rights reserved 319
320 Exergy

liquefied gases. At temperatures above the critical point, Linde-Hampson (LH) cycle, shown schematically and on
a substance exists in the gas phase only. The critical a T-s diagram in Figure 15.1, to illustrate energy and
temperatures of helium, hydrogen, and nitrogen are exergy analyses of liquefaction cycles. Makeup gas is
268 C, 240 C and 147 C, respectively. Therefore, mixed with the uncondensed portion of the gas from the
none of these substances exist in liquid form at atmospheric previous cycle, and the mixture at state 1 is compressed by
conditions. Furthermore, low temperatures of this magnitude an isothermal compressor to state 2. The temperature is
cannot be obtained by ordinary refrigeration techniques. kept constant by rejecting compression heat to a coolant.
To avoid heat leaks into cryogenic storage tanks and The high-pressure gas is further cooled in a regenerative
transfer lines, high-performance materials are needed that counterflow heat exchanger by the uncondensed portion of
provide high levels of thermal insulation. A good under- gas from the previous cycle to state 3, and throttled to state
standing of thermal insulation is important for the devel- 4, which is a saturated liquidevapor mixture state. The
opment of efficient and low-maintenance cryogenic liquid (state 6) is collected as the desired product, and the
systems. vapor (state 5) is routed through the heat exchanger to cool
In todays world, cryogenics and low-temperature the high-pressure gas approaching the throttling valve.
refrigeration are taking on increasingly significant roles. Finally, the gas is mixed with fresh makeup gas, and the
From applications in the food industry, energy, and medical cycle is repeated.
technologies to transportation and the space shuttle, The refrigeration effect for this cycle may be defined as
requirements exist for cryogenic liquids to be stored and the heat removed from the makeup gas in order to turn into
transferred. a liquid at state 6. Assuming ideal operation for the heat
In this chapter, a comprehensive exergy analysis of exchanger (i.e., the gas leaving the heat exchanger and the
a multistage cascade refrigeration cycle used for natural gas makeup gas are at the same state as state 1, which is the
liquefaction as a cryogenic system, based on a report by compressor inlet state), the refrigeration effect per unit
Kanoglu (2002b), is presented. The multistage cascade mass of the liquefied gas is given by:
cryogenic system is described and an exergy analysis of the  
cycle components and the minimum work required for qL h1  h6 h1  hf per unit mass of liquefaction
liquefaction are provided. (15.1)
where hf is the specific enthalpy of saturated liquid that is
15.2 ENERGY AND EXERGY ANALYSES OF withdrawn. From an energy balance on the cycle, the
GAS LIQUEFACTION SYSTEMS refrigeration effect per unit mass of the gas in the cycle may
be expressed as:
Several cycles, some complex and others simple, exist
for the liquefaction of gases. Here, we consider the qL h1  h2 per unit mass of gas in the cycle (15.2)

FIGURE 15.1 Schematic and temperature-entropy dia- 2


gram for a simple LH liquefaction cycle. q

Compressor win

2 1
T
Makeup
Heat
gas
exchanger

3 3
Expansion
valve 5
6 4 5
4

6 Liquid
removed
Chapter | 15 Exergy Analysis of Cryogenic and Liquefaction Systems 321

The maximum liquefaction occurs when the difference destruction during the processes. The reversible work for
between h1 and h2 (i.e., the refrigeration effect) is maxi- the simple LH cycle shown in Figure 15.1 may be
mized. The ratio of Equations 15.2 and 15.1 is the fraction expressed by the stream exergy difference of states 1
of the gas in the cycle that is liquefied, y. That is, and 6 as:
h1  h2 wrev ex6  ex1 h6  h1  T0 s6  s1 (15.10)
y (15.3)
h1  hf where state 1 has the properties of the makeup gas, which is
An energy balance on the heat exchanger gives: essentially the dead state. This expression gives the
minimum work requirement for the complete liquefaction
h2  h3 xh1  h5 of a unit mass of the gas. Exergy efficiency may be defined
where x is the quality of the mixture at state 4. Then the as the reversible work input divided by the actual work
fraction of the gas that is liquefied may also be determined input, both per unit mass of the liquefaction:
from: wrev h6  h1  T0 s6  s1
j (15.11)
y 1x (15.4) wactual 1=yh2  h1  T1 s2  s1 
An energy balance on the compressor gives the work of We present a numerical example for the simple LH
compression per unit mass of the gas in the cycle as: cycle shown in Figure 15.1. It is assumed that the
win h2  h1  T1 s2  s1 (15.5) compressor is reversible and isothermal; the heat exchanger
has an effectiveness of 100% (i.e., the gas leaving the liquid
The last term in this equation is the isothermal heat rejec- reservoir is heated in the heat exchanger to the temperature
tion from the gas as it is compressed. Assuming air behaves of the gas leaving the compressor); the expansion valve is
as an ideal gas during this isothermal compression process, isenthalpic; and there is no heat leak to the cycle. The gas is
the compression work may also be determined from: air, at 25 C and 1 atm at the compressor inlet and at 20 MPa
win RT1 lnP2 =P1 (15.6) at the compressor outlet. With these assumptions and
specifications, the various properties at the different states
The coefficient of performance (COP) of this ideal cycle is of the cycle and the performance parameters discussed
then given by: earlier are determined to be the following:
qL h1  h2
COP (15.7) h1 298.4 kJ/kg s1 6.86 kJ/kg K qL 34.9 kJ/kg gas
win h2  h1  T1 s2  s1
h2 263.5 kJ/kg s2 5.23 kJ/kg K wm 451 kJ/kg gas
In liquefaction cycles, an efficiency parameter used is
h3 61.9 kJ/kg sf 2.98 kJ/kg K COP 0.0775
the work consumed in the cycle for the liquefaction of
a unit mass of the gas. This is expressed as: h4 61.9 kJ/kg T4 194.2 C wm 5481 kJ/kg liquid
h5 78.8 kJ/kg x4 0.9177 wrev 733 kJ/kg liquid
h2  h1  T1 s2  s1
win per mass liquefied (15.8) hf 126.1 kJ/kg y 0.0823 j 0.134
y
As the liquefaction temperature decreases, the work
consumption increases. Noting that different gases have The properties of air and other substances are obtained
different thermophysical properties and require different using EES software (Klein, 2006). This analysis is repeated
liquefaction temperatures, this work parameter should not for different fluids and the results are listed in Table 15.1.
be used to compare the work consumptions of the lique- We observe in Table 15.1 that, as the boiling temper-
faction of different gases. A reasonable use is to compare ature decreases, the fraction of the gas that is liquefied, the
the different cycles used for the liquefaction of the same gas. COP, and the exergy efficiency decrease. The exergy
Engineers are usually interested in comparing the actual efficiency values are low, indicating significant potential
work used to obtain a unit mass of liquefied gas and the for improving performance, and thus decreasing the need
minimum work requirement to obtain the same output. for work consumption. Noting that the cycle considered in
Such a comparison may be performed using the Second this numerical example involves a reversible isothermal
Law. For instance, the minimum work input requirement compressor and a 100% effective heat exchanger, the
(reversible work) and the actual work for a given set of exergy efficiency figures here are optimistic. In practice,
processes may be related to each other by: an isothermal compression process may be approached
using a multistage compressor. For a high effectiveness,
wactual wrev T0 sgen wrev exdest (15.9)
the size of heat exchanger must be large, meaning a higher
where T0 is the environment temperature, sgen is the total cost. The work consumption may be decreased by
entropy generation, and exdest is the total exergy replacing the expansion valve with a turbine. Expansion in
322 Exergy

TABLE 15.1 Performance Parameters for a Simple LH Cycle for Various Fluids

Nitrogen Air Fluorine Argon Oxygen Methane


Liquefaction temperature 195.8 194.2 188.1 185.8 183.0 161.5
T4 ( C)
Fraction liquefied 0.0756 0.0823 0.0765 0.122 0.107 0.199
y
Refrigeration effect 32.6 34.9 26.3 33.2 43.3 181
qL (kJ/kg gas)
Specific work input 468 451 341 322 402 773
win (kJ/kg gas)
COP 0.0697 0.0775 0.0771 0.103 0.108 0.234
Specific work input 6193 5481 4459 2650 3755 3889
win (kJ/kg liquid)
Minimum specific work input 762 733 565 472 629 1080
wrev (kJ/kg liquid)
Exergy efficiency 12.3 13.4 12.7 17.8 16.8 27.8
j (%)

a turbine usually results in a lower temperature with the exergy efficiency for various gases. These figures are
respect to an expansion valve while producing work, and obtained using the cycle in Figure 15.1. As the liquefaction
thus decreasing the total work consumption in the cycle. temperature increases the liquefied mass fraction, the COP
The complexity and added cost associated with using and the exergy efficiency increase.
a turbine as an expansion device is only justified in large
liquefaction systems (Kanoglu, 2001, 2002b). In some
systems, both a turbine and an expansion valve are used to 15.3 EXERGY ANALYSIS OF A MULTISTAGE
avoid problems associated with liquid formation in the CASCADE REFRIGERATION CYCLE FOR
turbine.
The effect of liquefaction temperature on the liquefied
NATURAL GAS LIQUEFACTION
mass fraction and COP is illustrated in Figure 15.2, while An exergy analysis is presented of a multistage cascade
Figure 15.3 shows the effect of liquefaction temperature on refrigeration cycle used for natural gas liquefaction, based

FIGURE 15.2 Variation of liquefied mass fraction 0.122 0.24


and COP with liquefaction temperature for oxygen.
0.12 0.22
0.118
0.2
0.116
0.18
0.114
COP

0.16
y

0.112
0.14
0.11
0.12
0.108

0.106 0.1

0.104 0.08
-190 -180 -170 -160 -150 -140
T liq [C]
Chapter | 15 Exergy Analysis of Cryogenic and Liquefaction Systems 323

0.2 FIGURE 15.3 Relation between exergy efficiency and lique-


faction temperature for various gases.
0.19 argon

0.18
oxygen
0.17

0.16

0.15
air
0.14 fluorine

0.13 nitrogen

0.12
-200 -190 -180 -170 -160 -150 -140
Tliq (C)

on a report by Kanoglu (2002b). Multistage cascade 15.3.2 Description of the Cycle


refrigeration is described and an exergy analysis of the
cycle components and the minimum work required for Figure 15.4 shows a schematic of the cascade refrigeration
liquefaction are provided. cycle and its components. The cycle consists of three
subcycles, each using a different refrigerant. In the first
cycle, propane leaves the compressor at a high temperature
15.3.1 Background and pressure and enters the condenser, where cooling water
or air is used as a coolant. The condensed propane enters an
Natural gas is a mixture of methane (60%e98%), small
expansion valve, where its pressure is decreased to the
amounts of other hydrocarbons, and various amounts of
evaporator pressure. As the propane evaporates, the heat of
nitrogen, carbon dioxide, helium, and other trace gases.
evaporation comes from the condensing ethane, cooling
Natural gas can be stored as compressed natural gas at
methane, and cooling natural gas. Propane leaves the
pressures of 16e25 MPa and around room temperature, or
evaporator and enters the compressor, thus completing the
as liquefied natural gas (LNG) at pressures of 70e500 kPa
cycle.
and temperatures of around 160 C or lower. Natural gas
The condensed ethane expands in an expansion valve
can be transported as a gas in pipelines or as a liquid. In the
and evaporates as methane condenses and natural gas is
latter case, the gas is liquefied using unconventional
further cooled and liquefied. Finally, the methane expands
refrigeration cycles and then transported, often by marine
and evaporates as natural gas is liquefied and subcooled. As
ships in specially made insulated tanks. It is returned to
methane enters the compressor to complete the cycle, the
a gaseous state in receiving stations for end use.
pressure of the LNG is dropped in an expansion valve to the
Several refrigeration cycles, working on different
storage pressure. The three refrigerant cycles have multi-
refrigerants, can be used for natural gas liquefaction
stage compression and expansion, usually with three
including the mixed-refrigerant cycle, the cascade cycle,
stages, and, consequently, three evaporation temperature
and the gas expansion cycle. The first cycle used for natural
levels for each refrigerant. The mass flows in each stage are
gas liquefaction was a multistage cascade refrigeration
usually different.
cycle using three refrigerants (propane, ethane, or ethylene
Natural gas from the pipeline undergoes a process in
and methane) in the individual refrigeration cycles that
which acid gases are removed and pressure is increased to
make up the overall cycle.
an average value of 40 bar before entering the cycle.
Much work is consumed to produce LNG at about
160 C from natural gas at atmospheric temperature in the
gas phase (Finn et al., 1999). Reducing the work consumed 15.3.3 Exergy Analysis
in the cycle can help reduce the cost of LNG. Exergy
The exergy flow rate of a fluid in a control volume can be
analysis can help design, optimize, and assess such
written, neglecting kinetic and potential energies, as
systems, identifying the locations of exergy destruction,
follows:
thereby highlighting directions for potential improvement.
For such work-consuming processes, exergy analysis helps
determine the minimum work required for a desired result. _ mex
Ex _ _  h0  T0 s  s0 
mh (15.12)
324 Exergy

FIGURE 15.4 Schematic of a cascade refrigeration


cycle (showing only one stage for each refrigerant cycle
for simplicity). Condenser Propane
compressor

Cooling Expansion
water valve Ethane
Expansion compressor
valve
Evaporator Expansion
valve
Natural
gas LNG

Expansion
Evaporator- Evaporator- valve Methane
condenser I condenser II compressor

where T0 is the reference (dead) state temperature, h and s systems in the cycle. The first, evaporator-condenser I, is
are the specific enthalpy and entropy of the fluid at the the evaporator of the propane cycle and the condenser of
specified state, and h0 and s0 are the corresponding prop- the ethane and methane cycles. Similarly, evaporator-
erties at the dead state. Multiplying the specific flow exergy condenser II is the evaporator of ethane cycle and the
ex by the mass flow rate gives the exergy flow rate. condenser of methane cycle, The third system is the
The specific exergy change between two states (e.g., evaporator of the methane cycle and the fourth system is
inlet and outlet) can be expressed as: the condenser of the propane cycle, where cooling water is
used as a coolant. An exergy balance for an evaporator-
Dex h2  h1  T0 s2  s1 (15.13)
condenser expresses the exergy destroyed in the system as
Some exergy is lost during the process due to entropy the difference of the exergies of incoming and outgoing
generation. The specific irreversibility can be written as streams. For evaporator-condenser I,
i T0 Ds T0 sgen , where sgen is the entropy generation.
Two main causes of entropy generation in the process are hX X
I_ Ex _ out
_ in  Ex m_ p exp m_ e exe
friction and heat transfer across a finite temperature
difference. Heat transfer is generally accompanied by X i
exergy transfer, which is given by: m_ m exm m_ n exn
Z   in
T0 hX X
exq dq 1  (15.14)  m_ p exp m_ e exe
T
where dq is differential heat transfer and T is the source X i
temperature where heat transfer takes place. Heat transfer is m_ m exm m_ n exn
out
assumed to occur in surroundings at T0. If the transferred (15.15)
heat is lost; Equation 15.14 expresses a thermal exergy loss.
The exergy destruction and exergetic efficiency where the subscripts in, out, p, e, m, and n denote inlet,
expressions are presented below for the cycle components outlet, propane, ethane, methane, and natural gas,
in Figure 15.4. respectively. The summations account for the fact that
there are three stages in each refrigerant cycle with
different pressures, evaporation temperatures, and mass
flow rates.
15.3.3.1 Evaporators and Condensers
The exergetic efficiency of a heat exchanger can be
The evaporators and condensers in the system are treated as defined as the ratio of total outgoing stream exergies to total
heat exchangers. There are four evaporator-condenser incoming stream exergies. For evaporator-condenser I,

P  P P
m_ p exp out m_ e exe out m_ m exm out m_ n exn out
P  P P (15.16)
m_ p exp in m_ e exe in m_ m exm in m_ n exn in
Chapter | 15 Exergy Analysis of Cryogenic and Liquefaction Systems 325

An alternate definition for the exergy efficicency of a heat 15.3.3.1.1 Compressors


exchanger is the ratio of the increase in the exergy of the There is one multistage compressor in the cycle for each
cold fluid to the decrease in the exergy of the hot fluid refrigerant. The total work consumed in the cycle is the sum
(Wark, 1995). For evaporator-condenser I, the only fluid of work inputs to the compressors. The minimum work
with an exergy increase is propane, while the exergies of input for the compressor occurs when no irreversibilities
ethane, methane, and natural gas decrease. Therefore, the occur and exergy destruction is correspondingly zero. In
alternate efficiency can be written as: reality, irreversibilities occur due to friction, heat loss, and

P  P 
m_ p exp out  m_ p exp in
P P P P (15.17)
m_ e exe in  m_ e exe out m_ m exm in  m_ m exm out m_ n exn in  m_ n exn out

The values of efficiencies calculated using these two other dissipative effects. The exergy destructions in the
approaches are usually similar. In this analysis, the second propane, ethane, and methane compressors, respectively,
approach is used. can be expressed as:
The exergy destruction rate and exergy efficiency for _ in  Ex _ out
I_p Ex
evaporator-condenser II are expressible as: X  X 
m_ p exp in W_ p; in  m_ p exp out (15.24a)
I_ E_ in  E_ out
hX X i
m_ e exe m_ m exm m_ n exn I_e Ex
_ in  Ex _ out
hX X
in
i X X
 m_ e exe m_ m exm m_ n exn m_ e exe in W_ e; in  m_ e exe out (15.24b)
out
(15.18)
I_m Ex
_ in  Ex_ out
X X
P P m_ m exm in W_ m; in  m_ m exm out (15.24c)
m_ e exe out  m_ e exe in
j P P
m_ m exm in  m_ m exm out m_ n exn in  m_ n exn out where W_ p; in ; W_ e; in ; and W_ m; in are the actual power
(15.19) inputs to the propane, ethane, and methane compressors,
respectively. The exergy efficiency of a compressor can be
The exergy destruction rate and exergy efficiency can defined as the ratio of the minimum work input to the actual
be written for the evaporator of the methane cycle as: work input. The minimum work is simply the exergy
I_ Ex
_ in  Ex_ out difference between the actual inlet and exit states. Applying
hX i this definition to the propane, ethane, and methane
m_ m exm m_ n exn compressors, the respective exergy efficiencies become:
hX
in
i P  P 
 m_ m exm m_ n exn (15.20) m_ p exp out  m_ p exp in
jp (15.25a)
out
W_ p; in
P P
m_ m exm out  m_ m exm in P P
j (15.21) m_ e exe out  m_ e exe in
m_ n exn in  m_ n exn out je (15.25b)
W_ e; in
and for the condenser of propane cycle as:
P P
m_ m exm out  m_ m exm in
jm (15.25c)
I_ Ex
_ in  Ex_ out W_ m; in
h X  i
m_ p exp m_ w exw
in
h X  i
 m_ p exp m_ w exw (15.22) 15.3.3.1.2 Expansion Valves
out
In addition to the expansion valves in the refrigerant cycles,
m_ w exw out  m_ w exw in an expansion valve is used to reduce the pressure of LNG to
j P  P  (15.23) the storage pressure. Expansion valves are essentially
m_ p exp in  m_ p exp out
isenthalpic devices with no work interaction and negligible
where the subscript w denotes water. heat interaction with the surroundings. Exergy balances can
326 Exergy

be used to write the exergy destruction rates for the


W_ min
propane, ethane, methane, and LNG expansion valves: j (15.30)
X  X  W_ actual
_ in  Ex
I_p Ex _ out m_ p exp in  m_ p exp out
where W_ min is the minimum work input to the cycle, which
(15.26a) represents the minimum work for the liquefaction process.
X X
I_e Ex
_ in  Ex
_ out m_ e exe in  m_ e exe out
15.3.4 Minimum Work for the Liquefaction
(15.26b) Process
X X
I_m Ex
_ in  Ex
_ out m_ m exm in  m_ m exm out The exergy efficiency of the natural gas liquefaction
process can be defined as the ratio of the minimum work
(15.26c) required to produce a certain amount of LNG to the actual
X X work input. An exergy analysis on the cycle permits the
I_n Ex
_ in  Ex
_ out m_ n exn in  m_ n exn out minimum work input to be determined. The liquefaction
(15.26d) process essentially involves the removal of heat from the
natural gas. Therefore, the minimum work for the lique-
The exergy efficiency of an expansion valve can be defined faction process can be determined utilizing a reversible or
as the ratio of the total exergy output to the total exergy Carnot refrigerator. The minimum work input is simply the
input. The exergy efficiencies for the expansion valves work input required for the Carnot refrigerator for a given
considered here are thus: heat removal, and can be expressed as:
P 
Z  
m_ p exp out T0
jp P  (15.27a) wmin dq 1  (15.31)
m_ p exp in T
P where dq is the differential heat transfer and T is the
m_ e exe out
je P (15.27b) instantaneous temperature at the boundary where the heat
m_ e exe in transfer takes place. Note that T is smaller than T0 for
P a liquefaction process and to yield a positive work input, the
m_ m exm out sign of heat transfer must be negative since it is a heat
jm P (15.27c)
m_ m exm in output. The evaluation of Equation 15.31 requires
P a knowledge of the functional relationship between the heat
m_ n exn out transfer dq and the boundary temperature T, which is
jn P (15.27d)
m_ n exn in usually not available.
As seen in Figure 15.4, natural gas flows through three
evaporator-condenser systems in the multistage refrigeration
cycle before it is fully liquefied. Thermodynamically, this
15.3.3.2 Overall Cycle three-stage heat removal from natural gas can be accom-
The exergy destruction in the overall cycle is the sum of plished using three Carnot refrigerators, as seen in
exergy destruction in all internal devices (i.e., condensers, Figure 15.5a. The first Carnot refrigerator receives heat from
evaporators, compressors, and expansion valves). This the natural gas and supplies it to the heat sink at T0 as the
cycle exergy destruction can be obtained using the natural gas is cooled from T1 to T2. Similarly, the second
preceding exergy destruction expressions. The exergy Carnot refrigerator receives heat from the natural gas and
efficiency of the overall cycle can be defined as: supplies it to the heat sink at T0 as the natural gas is cooled
from T2 to T3. Finally, the third Carnot refrigerator receives
_ out  Ex
Ex _ in W_ actual  I_total
j (15.28) heat from the natural gas and supplies it to the heat sink at T0
_
W actual W_ actual as the natural gas is further cooled from T3 to T4, where it exits
where the numerator expresses the exergy difference (or the as LNG. The work rates required by the first, second, and
actual work input to the cycle W_ actual less the total exergy third Carnot refrigerators respectively can be determined as:
_ The actual work input to the overall cycle is
destruction I).  
the sum of the work inputs to the propane, ethane, and W_ 1 m_ n ex1  ex2 m_ n h1  h2  T0 s1  s2 
methane compressors as follows: (15.32a)
 
W_ actual W_ p; in W_ e; in W_ m; in (15.29) W_ 2 m_ n ex2  ex3 m_ n h2  h3  T0 s2  s3 
The exergy efficiency of the cycle can also be expressed as: (15.32b)
Chapter | 15 Exergy Analysis of Cryogenic and Liquefaction Systems 327

(a) FIGURE 15.5 Determination of minimum work for (a) the


cycle considered and (b) an equivalent system in terms of
initial and final states.

(b)

W_ 3 m_ n ex3  ex4 m_ n h3  h4  T0 s3  s4 
Q_ m_ n h1  h4 (15.34)
(15.32c)
For the inlet and exit states of natural gas described
The total power input, which expresses the minimum power above, the heat removed from the natural gas can be
input for the liquefaction process, is the sum of the above determined from Equation 15.34 to be 823.0 kJ/kg. That
terms: is, the removal of 823.0 kJ/kg of heat from the natural gas
W_ min W_ 1 W_ 2 W_ 3 m_ n ex1  ex4 requires a minimum of 456.8 kJ/kg of work. Since the
ratio of heat removed to work input is defined as the COP
m_ n h1  h4  T0 s1  s4  (15.33) of a refrigerator, this corresponds to a COP of 1.8. This
This minimum power can alternatively be obtained using relatively low COP of the Carnot refrigerator used for
a single Carnot refrigerator that receives heat from the natural natural gas liquefaction is expected due to high differ-
gas and supplies it to a heat sink at T0 as the natural gas is ence between the temperatures T and T0 in Equation
cooled from T1 to T4. Such a Carnot refrigerator is equivalent 15.31. An average value of T can be obtained from the
to the combination of three Carnot refrigerators shown in definition of the COP for a Carnot refrigerator, which is
Figure 15.5b. The minimum work required for the liquefac- expressed as:
tion process depends only on the properties of the incoming 1
COPR; rev (15.35)
and outgoing natural gas and the ambient temperature T0. T0 =T  1
A numerical value of the minimum work can be
calculated using typical values of incoming and outgoing Using this equation with COP 1.8 and T0 25 C, we
natural gas properties. When entering the cycle, the pres- determine T 81.3 C. This is the temperature a heat
sure of the natural gas is around 40 bar and the temperature reservoir would have if a Carnot refrigerator with a COP of
is approximately the same as the ambient temperature, that 1.8 operated between this reservoir and another reservoir at
is, T1 T0 25 C. Natural gas leaves the cycle liquefied at 25 C. Note that the same result could be obtained by
about 4 bar and 150 C. Since the natural gas in the cycle writing Equation 15.31 in the form:
usually consists of more than 95% methane, it is assumed  
T0
for simplicity that the thermodynamic properties of natural wmin q 1  (15.36)
T
gas are the same as those for methane. Using these inlet and
exit states, the minimum work input to produce a unit mass where q 823.0 kJ/kg, wmin 456.8 kJ/kg, and T0 25 C.
of LNG can be determined from Equation 15.33 as 456.8 We now investigate how the minimum work changes
kJ/kg. The heat removed from the natural gas during the with natural gas liquefaction temperature. We take the inlet
liquefaction process is determined from: pressure of natural gas to be 40 bar, the inlet temperature to
328 Exergy

be T1 T0 25 C, and the exit state to be saturated liquid JT valve is achieved with the turbine while producing
at the specified temperature. The properties of methane are power. Using the same typical values as before, we take the
obtained using EES software (Klein, 2006). Using the cryogenic turbine inlet state to be 40 bar and 150 C.
minimum work relation in Equaiton 15.33 and the revers- Assuming isentropic expansion to a pressure of 4 bar, the
ible COP relation in Equation 15.35, the plots in work output is calculated to be 8.88 kJ/kg of LNG. When
Figure 15.6 are obtained. this work is subtracted from the work input, this corre-
The minimum work required to liquefy a unit mass of sponds to a decrease of 2% in the minimum work input.
natural gas increases almost linearly with decreasing The use of a cryogenic turbine results in 4% extra LNG
liquefaction temperature, as shown in Figure 15.6. Obtain- production in an actual natural gas liquefaction plant
ing LNG at 200 C requires three times the minimum work (Verkoelen, 1996). Also, for the same inlet conditions, the
to obtain LNG at 100 C. Similarly, obtaining LNG at temperature of LNG at the cryogenic turbine exit is shown
150 C requires 1.76 times the minimum work to obtain to be lower than that at the expansion valve exit (Kanoglu,
LNG at 100 C. 2000b).
The COP of the Carnot refrigerator increases almost The main site of exergy destruction in the cycle is the
linearly with liquefaction temperature, as shown in compressors. Improvements to the exergy efficiencies of
Figure 15.6. The COP decreases almost by half when the the compressors will reduce the work input for the lique-
liquefaction temperature decreases from 100 C to faction process. Having three-stage evaporation for each
200 C. These figures show that the maximum possible refrigerant in the cascade cycle results in a total of nine
liquefaction temperature should be used to minimize the evaporation temperatures. Also, having multiple stages
work input. In other words, LNG should not be liquefied to makes the average temperature difference between the
lower temperatures than needed. natural gas and the refrigerants small. This results in
For the typical natural gas inlet and exit states specified a smaller exergy destruction in the evaporators since the
in the previous section, the minimum work is determined to greater the temperature difference, the greater the exergy
be 456.8 kJ/kg of LNG. A typical actual value of work destruction. As the number of evaporation stages increases,
input for a cascade cycle used for natural gas liquefaction is the exergy destruction decreases. However, adding more
given by Finn et al. (1999) to be 1188 kJ/kg of LNG. Then stages means additional equipment cost. More than three
the exergetic efficiency of a typical cascade cycle can be stages for each refrigerant is usually not justified.
determined from Equation 15.30 to be 38.5%. The actual
work input required depends mainly on the feed and
ambient conditions and the compressor efficiency. 15.4 EXERGY ANALYSIS OF AN
INTEGRATED HYDROGEN LIQUEFACTION
15.3.5 Discussion USING GEOTHERMAL ENERGY
Recent advances have made it possible to replace the Joule In this section, an exergy analysis is described of an
Thompson (JT) expansion valve of the cycle with a cryo- advanced conceptual system for hydrogen liquefaction.
genic hydraulic turbine. The same pressure drop as in the Liquefaction of hydrogen is of increasing interest (Kanoglu

FIGURE 15.6 Variation of minimum specific work and COP 800 2.4
with natural gas liquefaction temperature.

700 2.2

600 2.0
wmin [kJ/kg]

COP

500 1.8

400 1.6

300 1.4

200 1.2
-200 -180 -160 -140 -120 -100
T [C]
Chapter | 15 Exergy Analysis of Cryogenic and Liquefaction Systems 329

et al., 2010), in part because of hydrogens potential as an The power to the compressor in the LH cycle is
energy carrier. The system integrates a triple effect provided by a binary geothermal power plant with iso-
absorption cooling system (TEACS), which is used for butene as the working fluid (Figure 15.7d). The isobutene is
precooling to improve efficiency and economics, and an heated and vaporized using geothermal water from the
LH hydrogen liquefaction system. HTG at 20 C below the geothermal source temperature.
Geothermal energy drives the process. High-temperature This vaporized isobutene flows through the turbine, and is
geothermal resources (>150 C) are generally used for power then condensed and pumped back to the heat exchanger.
generation, while moderate-temperature (90 Ce150 C) and The turbine inlet and exit pressures are taken to be 3000 and
low-temperature (<90 C) resources are best suited for direct 400 kPa, respectively. The temperature at the turbine inlet
uses such as space and process heating, cooling, aquaculture, is taken to be 15 C below the geothermal water tempera-
and fish farming. Common types of geothermal power plants ture at the heat exchanger inlet. The geothermal water
include dry steam, single- and double-flash, binary, and flash/ exiting the isobutene heat exchanger passes to the HTG for
binary cycles (Kanoglu et al., 2010). Here, we consider heat recovery before it returns to the underground well.
a binary isobutene system for electricity generation using
a high-temperature geothermal source; the electricity drives
the LH system. 15.4.2 Analysis
Many types of absorption cooling systems are available, Mass and energy balances are written for the integrated
including lithium bromide/water chillers, which are suit- system and its components, and selected energy and exergy
able for space cooling, and ammonia/water systems, which parameters are evaluated, including binary system effi-
can provide industrial cooling to as low as 50 C (ASH- ciencies, TEACS COPs, and system utilization factors.
RAE, 2006). Single- and double-effect absorption cooling
systems are relatively well understood (Ziegler et al., 1993;
Dincer and Dost, 1996), and TEACS are being investigated
15.4.2.1 TEACS
(Ratlamwala et al., 2010, 2011a,b). Heat is provided to the HTG of the absorption cooling
system using geothermal water. The geothermal water loop
supplies the geothermal water from the binary system back
to the HTG for heat recovery. The rate of heat transfer from
15.4.1 System Description
the geothermal water source is expressible as follows:
The integrated system considered here is shown in  
simplified form in Figure 15.7a, and its three main Q_ geohigh m_ geo hgeosource  hgeoHTG exit (15.37)
subsystems are illustrated in Figure 15.7bed.  
In the TEACS using ammonia-water as working fluid Q_ geolow m_ geo hgeoHTG exit  hgeobinary exit (15.38)
(Figure 15.7b), thermal energy (heat) is provided to the high-
temperature generator (HTG) via the high-temperature The heat supply rate to the HTG is given by:
geothermal water from the underground reservoir and the
Q_ HTG Q_ geohigh Q_ geolow (15.39)
return geothermal water from the binary isobutene power
plant. The TEACS precools hydrogen in the evaporator from The exergy destruction in the HTG can be written as:
25 C to 16.4 C, at 1 atm.
Ex _ 30 Ex
_ HTG Ex _ 31  Ex
_ 29 (15.40)
The precooled hydrogen is fed to the LH liquefaction
cycle (Figure 15.7c). Makeup gas is mixed with the and similar relations are written for the other generators.
precooled uncondensed portion of the gas from the The rate of exergy into the evaporator is calculated as:
TEACS, and the mixture at state 1 (101 kPa) is
compressed to state 2 (10 MPa). Heat is removed from _ eva m_ 11 h10  h11  T0 s10  s11
Ex (15.41)
the compressed gas by a coolant. The high-pressure gas is
cooled to state 3 in a regenerative counterflow heat where T0 is taken as 298.15 K. The energetic and exergetic
exchanger (I) by the uncondensed gas, and is cooled COPs are expressed as follows:
further by flowing through two nitrogen baths (II and IV)
and two regenerative heat exchangers (III and V) before
Q_ eva
being throttled to state 8, where it is a saturated liquid- COPen (15.42)
evapor mixture. The liquid hydrogen product exits and Q_ geo w_ p
the vapor is routed through the bottom half of the cycle.
After, supplying heat in a regenerative heat exchanger, _ eva
Ex
COPex (15.43)
the gas is mixed with fresh makeup gas from the TEACS _
Exgeo w_ p
and the cycle repeats.
330 Exergy

FIGURE 15.7 Schematic diagrams of (a) the integrated system, (b) triple effect absorption cooling subsystem,
(c) LH subsystem, and (d) binary power plant subsystem.

where w_ p denotes pump power. The exergy efficiency of the The power consumed by pump in binary cycle and
absorption cooling system is defined as: parasitic losses, respectively, can be expressed as:

jabs
COPen
(15.44) W_ p iso m_ iso h2  h1 (15.46)
COPex
 
_ parasitic 0:2 W_ turb  W_ p iso
W (15.47)
15.4.2.2 Binary Power Plant so the net power from the binary isobutene plant can be
The electrical power produced by the turbine of the binary expressed as:
isobutene plant is as follows:
W_ turb m_ iso h3  h4 (15.45) W_ netgeo W_ turb  W_ p iso  W_ parasitic (15.48)
Chapter | 15 Exergy Analysis of Cryogenic and Liquefaction Systems 331

FIGURE 15.7 (Continued)

_ H2 m_
En   (15.52)
15.4.2.3 LH Liquefaction Cycle H2liquefied hH2  hH2
f 0
The ideal specific work required to compress hydrogen
from P1 to P2 is given as follows:
p2 m_ H2liquefied fliq m_ H2 (15.53)
wcompideal RT0 ln (15.49)
p1
However, the actual specific work input to liquefaction
_ H2
Ex
cycle per unit mass of hydrogen is: ufex (15.54)
_ geoHigh w_ compactual
w_ p Ex
wcompideal
wcompactual (15.50)
hcomp
h   i
Here, P1 101 kPa and P2 10 MPa, hcomp is 65%, _ H2 m_ H2
Ex hH2f  hH20  T0 sH2f  sH20
liquefied
and the electricity needed for nitrogen is taken to be 5050
kJ/kg (Nandi and Sarangi, 1993). (15.55)

15.4.2.4 Utilization Factors 15.4.3 Performance


The energetic and exergetic utilization factors of the inte- The performance is determined for the TEACS, the binary
grated system are expressible as follows: power plant, the LH liquefaction system, and the overall
E_ nH2 system. Given the importance of geothermal energy as the
ufen (15.51) driver of the integrated system, the performance parameters
_
w_ p QgeoHigh w_ compactual
are determined as a function of mass flow rate and
where temperature of the geothermal water source.
332 Exergy

FIGURE 15.8 Effect of geothermal water mass flow 1.6 1.6


rate on energetic and exergetic COP. COPen at Qcon = 300 kW COPex at Qcon = 300 kW
COPen at Qcon = 320 kW COPex at Qcon = 320 kW
COPen at Qcon = 340 kW COPex at Qcon = 340 kW
1.2 1.2

Tgeo = 473 K

COPex
0.8 0.8

COPen
0.4 0.4

0 0
1.5 1.8 2.1 2.4 2.7 3
mgeo [kg/s]

15.4.3.1 Performance Variations with The increase in energy input to the TEACS and
Geothermal Mass Flow Rate decrease in cooling load with increase in m_ geo lowers the
energetic and exergetic COPs of the TEACS, as shown in
An increase in the mass flow rate of geothermal water m_ geo Figure 15.8. The energetic and exergetic COPs vary from
results in higher energy input to the TEACS. This results in 1.4 to 0.12 and 1.0 to 0.08, respectively, with increasing
a lower output from the evaporator in form of cooling load m_ geo . The decrease in the COPs is a direct result of higher
for a fixed condenser load. The energy input to the HTG energy input to the system and the lower output from the
increases from 185 to 370 kW as m_ geo increases from 1.5 to system in the form of cooling load. Also, the increase in
3.0 kg/s. The cooling load of the TEACS varies from 268.2 m_ geo results in a higher TEACS exergy efficiency and
to 43.6 kW as m_ geo increases from 1.5 to 3.0 kg/s for a higher net work output from the geothermal power plant.
a varying condenser load from 300 to 340 kW and for a fixed Exergy efficiency and net work output increase from 0.69
geothermal source temperature of 473 K. As the condenser to 0.70 and 69.7 to 139.4 kW, respectively, with increasing
load increases, the evaporator load rises because of a higher m_ geo (see Figure 15.9). This behavior results because an
heat rejection from the flow exiting the generator. This increase in m_ geo for a fixed temperature difference results in
higher heat rejection lowers the temperature of the input flow a higher energy input to the TEACS and a higher work
to the evaporator and therefore increases the cooling load. output from the binary power plant.

FIGURE 15.9 Effect of geothermal water mass 0.71 150


flow rate on Second Law efficiency of TEACS and
net work output of the binary power plant. 135

120
0.7
105
Wnet,geo
abs

Tgeo = 473 K 90

75
0.69
60

45

0.68 30
1.5 1.8 2.1 2.4 2.7 3
mgeo [kg/s]
Chapter | 15 Exergy Analysis of Cryogenic and Liquefaction Systems 333

0.1 0.24 FIGURE 15.10 Effect of geothermal water mass


ufen at Qcon = 300 kW flow rate on utilization factor.
0.09 0.22
ufen at Qcon = 320 kW
ufen at Qcon = 340 kW 0.2
0.08
0.18
0.07 ufex at Qcon = 300 kW
ufex at Qcon = 320 kW 0.16
0.06 ufex at Qcon = 340 kW 0.14

ufex
ufen

0.05 Tgeo = 473 K 0.12

0.04 0.1
0.08
0.03
0.06
0.02
0.04
0.01 0.02
0 0
1.5 1.8 2.1 2.4 2.7 3
mgeo [kg/s]

The energetic and exergetic utilization factors vary from the energy transfer to the HTG of TEACS by increasing the
0.06 to 0.009 and from 0.006 to 0.21, respectively, with temperature difference. This increase in energy input to the
increasing m_ geo (see Figure 15.10). This trend occurs because TEACS lowers the output from the TEACS cooling load for
increasing m_ geo lowers the TEACS cooling load and thus a fixed condenser load, decreasing the TEACS COPs.
decreases the amount of hydrogen gas precooled, which
ultimately decreases the amount of hydrogen gas liquefied.
15.4.4 Further Discussion and Findings
15.4.3.2 Performance Variations with
The analysis confirms, in general, that renewable energy
Geothermal Source Temperature
systems can be environmentally benign, efficient, and
Increasing the geothermal water source temperature Tgeo sustainable, and that the integrated system considered
reduces the energetic and exergetic COPs of the TEACS provides an attractive hydrogen liquefaction option in
(see Figure 15.11). The energetic and exergetic COPs vary terms of energy consumption, greenhouse gas emissions,
from 0.82 to 0.67 and from 0.59 to 0.09, respectively, as and other factors. This system can be modified for lique-
Tgeo increases from 570 to 630 K for varying condenser fying other gases. The key observations regarding the effect
loads of 300, 320, and 340 kW and for m_ geo 2.0 kg/s. of geothermal parameters on the integrated system
Increasing the geothermal source water temperature raises considered here include:

0.9 0.78 FIGURE 15.11 Effect of geothermal water


COPen at Qcon = 300 kW COPex at Qcon = 300 kW source temperature on energetic and exergetic
COPen at Qcon = 320 kW COPex at Qcon = 320 kW COPs.
0.85 COPen at Qcon = 340 kW COPex at Qcon = 340 kW 0.72

0.8 0.66
mgeo = 2.0 kg/s
COPex

0.75 0.6
COPen

0.7 0.54

0.65 0.48

0.6 0.42
570 580 590 600 610 620 630
Tgeo [K]
334 Exergy

l The cooling load, energetic and exergetic COPs, described in this chapter be used for hydrogen
amounts of hydrogen gas precooled and liquefied, and liquefaction? If not, what modifications would
energetic and exergetic utilization factors decrease as be needed to allow for hydrogen liquefaction?
the mass flow rate of geothermal water increases. Which cycles are currently used for hydrogen
l The energy input to the TEACS HTG, the TEACS liquefaction?
exergy efficiency, and the net work of the binary power 15.11 Can an absorption cooling system be used for gas
system increase as the mass flow rate of geothermal liquefaction? Explain.
water increases. 15.12 Compare the work required to compress a gas in
l The energetic and exergetic COPs decrease as the a gas liquefaction cycle using (a) an isothermal
geothermal water source temperature increases. compressor and (b) an isentropic compressor.
15.13 Do you favor replacing the expansion valve with
a turbine in a gas liquefaction system? Explain from
15.5 CLOSING REMARKS an exergetic perspective.
Exergy analyses of cryogenic systems, particularly gas 15.14 Provide some guidelines in the selection of refrig-
liquefaction systems, have been described and studied for erants for use in oxygen, methane, and hydrogen
various integrated systems. Exergy analysis is particularly liquefaction systems?
important for cryogenic and liquefaction applications, 15.15 Investigate the use of cryogenic turbines in natural
because the exergy of a cryogenic fuel becomes increas- gas liquefaction systems.
ingly significant as its temperature decreases well below the 15.16 Which components of the natural gas liquefaction
environment temperature. system considered in this chapter involve greater
exergy destructions? Provide methods for reducing
or minimizing exergy losses.
PROBLEMS 15.17 Obtain a published article on exergy analysis of
15.1 What is the difference between a refrigeration a gas liquefaction system. Using the operating data
system and a gas liquefaction system? Which provided in the article, perform a detailed exergy
system typically involves higher exergy destruction analysis of the system and compare your results to
and thus lower exergy efficiency? those in the original article. Also, investigate the
15.2 Compare the following processes: (a) transportation effect of varying important operating parameters on
of natural gas in the pipelines and (b) liquefying the the system exergetic performance.
natural gas and then transporting it in tanks. 15.18 Obtain actual operating data from a gas liquefaction
15.3 Compare the following processes from an exergetic system and perform a detailed exergy analysis.
point of view: (a) transportation of natural gas as Discuss the results and provide recommendations
a gas in tanks and (b) liquefying the natural gas and based on the exergy results for improving the
then transporting it in tanks. efficiency.
15.4 How can you express the COP and exergy efficiency 15.19 Consider the system shown in Figure 15.4. Conduct
of a gas liquefaction process? Can the COP and detailed exergy analysis of the system to create a bar
exergy efficiency be greater than 1? chart showing how much exergy is destroyed in
15.5 Provide three alternative definitions of exergy effi- each component of the system. Also, make a bar
ciency for a gas liquefaction system. chart showing the percentage of exergy destruction
15.6 Write an expression for the minimum work for the in each component of the system.
liquefaction of a gas. What is the relationship between 15.20 Consider the integrated system shown in
this expression and the exergy of the heat removed Figure 15.7a. Conduct detailed exergy analysis of
from the gas during the liquefaction process? the system to create a bar chart showing how much
15.7 Which is greater in a gas liquefaction system: the exergy is destroyed in each component of the
heat removal per unit mass of the gas or the heat system. Also, make a bar chart showing the per-
removal per unit mass of liquefaction? Can one be centage of exergy destruction in each component of
determined from the other? the system.
15.8 How does the exergy efficiency of a gas liquefaction 15.21 For the integrated system shown in Figure 15.7a,
system change with liquefaction temperature? replace the working fluid of TEACS and a binary
15.9 Investigate various cycles used for gas liquefaction system with lithium-bromide-water and ammonia,
and compare them from an exergetic perspective. respectively. Conduct energy and exergy analyses and
15.10 What is the importance of liquefying hydrogen for compare your results with the results provided in this
a future hydrogen economy? Can the LH process chapter.

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