Energy Conversion & Management 40 (1999) 15151525

Characteristics and applications of the cold heat exergy of

liqueed natural gas
Hongtan Liu*, Lixin You
Department of Mechanical Engineering, University of Miami, Coral Gables, FL 33124, USA
Received 29 June 1998; accepted 22 January 1999

Abstract

A mathematical model for predicting the low temperature exergy, pressure exergy and total cold heat
exergy of Liqueed Natural Gas (LNG) is developed in this paper. In the model, the liquid mixture
densities are calculated by a shape factor Corresponding State method, VaporLiquid-Equilibrium data
of LNG are predicted by an improved method and the inuences of real uid eects are considered. The
model is used to determine the various exergies, and the inuences of ambient temperature, system
pressure and mixture component concentrations on the cold heat exergies are analyzed. Dierent
schemes for applying the low temperature exergy and pressure exergy are proposed. Based on the
modeling results, it is proposed that the schemes for applying the cold heat exergies of LNG be
determined by thermodynamic cycle optimization, while considering the magnitudes of low temperature
exergy and pressure exergy, as well as the required gas supply pressures. # 1999 Elsevier Science Ltd.
All rights reserved.

Keywords: Liqueed natural gas; LNG; Exergy; Cold heat; Power generation

1. Introduction

Natural gas is one of the most widely used conventional mineral energy resources. In
contrast to other mineral resources, such as coal and gasoline, natural gas has higher
combustion heat and produces much less pollution. The disadvantage is that it is in a gaseous
state under ambient temperature and pressure, so it usually must be liqueed to LNG for long

* Corresponding author. Tel.: +1-305-284-2571; fax: +1-305-284-2580.

E-mail address: hliu@miami.edu (H. Liu)

0196-8904/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 9 6 - 8 9 0 4 ( 9 9 ) 0 0 0 4 6 - 1
1516 H. Liu, L. You / Energy Conversion & Management 40 (1999) 15151525

distance transportation and storage. Besides being used as the fuel for power generating plants,
for city gases and as feeds for chemical engineering, LNG is very likely to be used as the fuel
for airplanes and new generations of rockets because of its high energy density (in contrast to
liquid hydrogen) and high specic impulse [1]. LNG is also a very promising fuel for ground
vehicles, either as direct fuel for engines or as fuel for fuel cells [2].
LNG is produced by cryogenic refrigeration of natural gas after removing the acid and
water. Liquefying natural gas is a high energy consumption process, producing one ton of
LNG consumes about 850 kWh of electric energy. In addition, it should be gasied for normal
use at the receiving site. Gasication also consumes energy. If we can make use of the cold
heat of LNG, it is evident that the overall eciency will improve. When the cold heat is used
for power generation, it is estimated that one ton of LNG will produce about 240 kWh of
electrical energy. Considering the large LNG consumption, the potential for power generation
using the LNG cold heat is very signicant and should be explored in practical applications.
Exergy analysis is an important method for analysis of energy systems. It can predict the
distribution, source and magnitude of irreversible losses in energy systems and hence, provide
guidelines for ecient energy usage [3]. Because both liquefaction of natural gas and
gasication of LNG are energy intensive processes, exergy analysis is indispensable for
designing highly ecient liquefaction and cold heat application systems.
LNG is a low temperature multicomponent liquid mixture. Its main component is methane,
whose concentration is usually above 80% in the mixture. It also contains nitrogen, ethane,
propane, normal butane and isobutane, normal pentane and isopentane. Its exergy depends on
the system pressure, temperature, ambient temperature and component concentrations. To
predict exergy, precise state parameter (density) and VaporLiquid-Equilibrium (VLE) data are
necessary. Based on the previous related work on LNG thermal properties [4,5], an exergy
model for LNG is developed, the inuences of various factors are analyzed and some cold heat
exergy application schemes are proposed.

2. Mathematical model of exergy analysis for LNG cold heat

According to the denition of exergy, the exergy is the maximum work potential of a given
form of energy with the environmental condition taken as the reference state. To facilitate the
discussions in this paper, the exergy can be decomposed into two parts: one is the low
temperature exergy Ex,th , which is dened as the thermal non-equilibrium exergy with the
environment under the system pressure, and the other is the pressure exergy Ex,p , which is
dened as the system pressure non-equilibrium exergy with the environment under the ambient
temperature. Thus, the total exergy of LNG is
Ex T,P Ex,th Ex,p 1

where
Ex,th Ex P,T Ex P,T0 2

Ex,p Ex P,T0 Ex P0 ,T0 3

 H. Liu, L. You / Energy Conversion & Management 40 (1999) 15151525 1517

When LNG is heated from the low temperature to ambient temperature, a boiling phase
change and apparent heating will occur consecutively. Suppose the average phase temperature
is Ts , then the vaporization latent heat exergy that LNG absorbed is TT0s 1r, where r is the
latent heat of evaporation. The apparent heat exergy that low temperature natural gas
T
absorbed from Ts to ambient temperature T0 is T0s Cp 1 TT0 dT. Thus, the total low
temperature exergy is the sum of the vaporization latent heat exergy and the apparent heat
exergy
  Ts  
T0 T0
Ex,th 1 r Cp 1 dT 4
Ts T0 T

The pressure exergy is

P,T0
Ex,p Ex P,T0 v dp 5
P0 ,T0

LNG is a low temperature multicomponent liquid mixture. Its latent heat and average
bubble temperature depend on its concentrations and the system pressure. The thermal
properties of both LNG and natural gas deviate from ideal gas properties, so a real uid state
equation must be used to predict the thermal properties and VLE properties of LNG.
The RedlichKwongSoave (RKS) equation is a three parameter real uid state equation.
Although it is simple in form, its precision is high in predicting the thermal properties of light
hydrocarbons. The present authors once used the equation to determine the thermal properties
such as the boiling point and vaporization latent heat of methane and nitrogen, and the results
are in very good agreement with the literature. The disadvantage is that the deviations in the
liquid density are high, so the liquid density in this paper is predicted by a shape factor
Corresponding State method which was described in a previous paper [4].
The RKS equation is [6]
RT aa
P 6
v b vv b

which can be expressed in polynomial form as

Z 3 Z 2 A B B 2 Z AB 0 7

When the equation is used for mixtures, the related coecients are
XX
aa yi yj aaij 8

X
b yi bi 9

XX
A yi yj Aij 10
1518 H. Liu, L. You / Energy Conversion & Management 40 (1999) 15151525
X
B y i Bi 11

q
aaij 1 kij aai aaj 12

p
A ij 1 kij Ai Aj 13

For multicomponent VLE, the temperature and pressure of each phase are equal, the
chemical potential of each component is equal, and the fugacity of each component in both
liquid phase and gas phase is also equal

f^ vi f^ li 14

or
v l
f^ i yi P f^ i x i P 15

Thus,
l
yi f^ i
Ki v 16
xi f^ i

where f^i ,f^ i are the fugacity and fugacity coecient of each component in the mixture.
Substituting the RKS equation into the fugacity equation,
" #  
^ Bi A Bi 2 X B
ln fi Z 1 lnZ B yi aaij ln 1 17
B B B aa j Z

For the vapor and liquid phases, Z,A,Bi ,B have dierent values, and the compressibility factor
of the liquid phase here is calculated by the shape factor Corresponding State method. When
the liquid component concentrations and system pressure are given, the respective bubble
temperature and vapor concentrations can be predicted using the VLE calculation.
The latent heat of evaporation is the enthalpy dierence between the vapor phase and liquid
phase. For real uids, the enthalpy can be predicted by the residual enthalpy function. The
residual enthalpy equation derived from the RKS equation is
"    #
id A D B
h h RT 1 Z 1 ln 1 18
B aa Z

where
XX
pp
D yi yj mj 1 kij ai ai aj Trj 19
i j

For equilibrium vapor and liquid phases, hid is the same, so the vaporization latent heat is the
 H. Liu, L. You / Energy Conversion & Management 40 (1999) 15151525 1519

dierence between two residual enthalpy functions

r hv hl hid h l hid h v 20
The real gas specic heat capacity is
CP C 0pm DCpm 21

where
X X

C 0pm yj C 0Pj yj Aj Bj T Cj T 2 Dj T 3 22
j j

@ Dh
DCpm 23
@T
where Aj ,Bj ,Cj ,Dj are constants of various components in the ideal gas specic heat capacity
equation, DCpm can be obtained by dierentiating the enthalpy dierence.
The low temperature exergy can be obtained by substituting Ts ,r,Cp into Eq. (4).
The pressure exergy of LNG is
P,T0 P,T0 P,T0 P,T0
 
Ex,p v dP dPv P dv Pv P0 v0 T0 P dv 24
P0 ,T0 P0 ,T0 P0 ,T0 P0 ,T0

Substituting the RKS equation into Eq. (24) and integrating

Fig. 1. The variation of the exergy of LNG with the ambient temperature (P 1:013 MPa).
1520 H. Liu, L. You / Energy Conversion & Management 40 (1999) 15151525
 
vb aa 1 b=v0
Ex,p RT0 Z 1 ln ln 25
v0 b bRT0 1 b=v T0

3. The characteristics of LNG cold heat exergy

Using the mathematical model developed in the last section, the inuences of various factors
such as ambient temperature, system pressure and component concentrations on the LNG cold
heat exergy can be determined. All calculations in this paper consider eight components:
methane, ethane, propane, n-butane, i-butane, n-pentane, i-pentane and nitrogen.

3.1. The inuence of ambient temperature

Fig. 1 shows the variation of cold heat exergy of one typical LNG mixture with ambient
temperature T0 . With the increase of ambient temperature, the low temperature exergy, the
pressure exergy and the total cold heat exergy increase. These results are in agreement with the
denition of exergy. It also means that the recovering eciency of LNG cold heat exergy
depends on the ambient temperature. The usable amount of LNG cold heat exergy increases
with ambient temperature.

3.2. The inuence of system pressure

Fig. 2 shows the variation of LNG cold heat exergy with system pressure. It is shown that

Fig. 2. Variation of the exergy of LNG with the system pressure (T0 283 K).
 H. Liu, L. You / Energy Conversion & Management 40 (1999) 15151525 1521

the pressure exergy increases with system pressure. This is again in agreement with the
denition of pressure exergy. However, the low temperature exergy decreases with the increase
of pressure. There are two main reasons here. One is that the bubble temperature of liquid
mixtures will increase with pressure, which decreases the temperature dierence to equilibrate
with the ambient temperature. The other is that the liquid mixture will come closer to the
critical point when the system pressure increases, which decreases the latent heat of
vaporization. The total cold heat exergy may be obtained by adding the low temperature
exergy with the pressure exergy. Fig. 2 shows the total exergy tends to decrease with the
increase of pressure, however, the decreasing tendency becomes slower when the system
pressure P > 2 MPa. Fig. 2 also shows the relative magnitude of the low temperature exergy
and the pressure exergy: when P<1:8 MPa, Ex,th > Ex,p ; when P > 1:8 MPa, Ex,p > Ex,th . The
result means that the relative magnitude of the cold heat exergy and the pressure exergy are
not constant. It is thus very important in practical applications because dierent
thermodynamic cycles should be used for recovering dierent exergies, which will be discussed
in detail later.

3.3. The inuence of LNG component concentrations

LNG is a multicomponent liquid mixture. Its exergy also depends on the component
concentrations. Because of the possible variation ranges of components and concentrations in
LNG mixtures, it will be dicult to distinguish the inuences of concentrations from other
inuencing factors. Thus, in the following discussion, LNG is considered to be a binary
mixture composed of only methane and ethane. Fig. 3 shows the variation of LNG cold heat
exergy with the methane concentration in the methane and ethane binary mixture. It can be

Fig. 3. The variation of exergy of LNG with the methane concentration (T0 283 K).
1522 H. Liu, L. You / Energy Conversion & Management 40 (1999) 15151525

seen that the low temperature exergy, the pressure exergy and the total cold heat exergy
increase with methane concentration under the same system pressure and ambient temperature.
There are also two reasons here. One is that under the same pressure, the bubble temperature
will decrease with the increase of methane concentration. As a result, the temperature
dierence between the system and the environment will increase, so the low temperature exergy
increases. The other is that with the increase of methane concentration, the molar mass of the
gas mixture decreases, and thus the pressure exergy increases. Since both low temperature
exergy and the pressure exergy increase with methane concentration, it is evident that the total
exergy will also increase.

4. The applications of LNG cold heat exergy

From the above discussions, it is shown that the cold heat exergy of LNG can be
decomposed into the low temperature exergy and the pressure exergy. The mechanism of using
these two dierent exergies for power generation is dierent. The application of the low
temperature exergy usually involves a Rankine power cycle using a low boiling temperature
working substance. In such cycles, sea water or other industry waste heat is used in the
evaporation process, LNG is used as the cold reservoir in the condensation process, and the
output work is done through an expanding process during which the high pressure vapor
expands through the steam turbine. The application of pressure exergy involves natural gas
direct expansion schemes. High pressure natural gas expands through the gas turbine, and the
output work is done through the expanding process. When the feed gas pressure is relatively
high, a multistage expanding cycle may be used.
Because the recovering principles for low temperature exergy and pressure exergy are
dierent, for practical LNG cold heat applications, it is important to know which kind of
exergy contributes most to the total cold heat exergy. If an unsuitable scheme is used, the
recovering eciency will be greatly decreased. When Ex,th  Ex,p , the Rankine power cycle is
more suitable to recover the cold heat of LNG. When Ex,p  Ex,th , natural gas direct
expansion is more suitable for recovering the available exergy. When Ex,th Ex,p , the mixed
cycle which combines the Rankine cycle and the gas direct expansion cycle may be used to
recover the cold heat exergy.

Fig. 4. Mixed cycle for LNG cold heat exergy application (medium pressure case).
 H. Liu, L. You / Energy Conversion & Management 40 (1999) 15151525 1523

There may be several mixed cycle schemes for recovering the LNG cold heat. Fig. 4 shows
one mixed cycle combining a one stage Rankine cycle and a one stage gas direct expansion
cycle. Turbine T1, evaporator E1, condenser E2 and pump P1 constitute the Rankine cycle, in
which propane may be used as the working substance. After owing through heat exchangers
E2 and E3A, the LNG is vaporized to a high pressure gas. When the high pressure gas
expands through the gas turbine T2, the output work is done, and the power is produced. The
expanded gas can be supplied to customers after further heating by E3B. The system has a one
stage natural gas direct expansion cycle, which is suitable for systems requiring medium gas
pressure (such as 2 MPa).
Fig. 5 shows a system combining a one stage Rankine cycle and a two stage natural gas
direct expansion cycle. Steam turbine T1, evaporator E1, condenser E2B and pump P1
constitute the Rankine cycle, in which propane can be used as the working substance. Gas
turbines T2 and T3 constitute a two stage natural gas direct expansion cycles. The discharge
gas from the rst stage turbine T2 is divided into two streams. The wet vapor portion gas
condenses to liquid through the heat exchanger E2A, and the condensed liquid goes into the
system and recirculates after pumping. After further heating, the dry vapor expands through
the second turbine and, then, may be supplied to customers. This kind of mixed cycle
comprises a two stage natural gas direct expansion cycle, which may make full use of the
pressure exergy of LNG cold heat, so it is suitable for the case when the required gas pressure
is low (such as 0.5 MPa).
Fig. 6 shows a system comprised of a one stage Rankine cycle and one natural gas
recirculation cycle. Steam turbine T1, evaporator E1, condenser E2B and pump P1 constitute
one Rankine cycle, and again, propane may be used as the working substance. After being
heated through the heat exchangers E2A, E2B and E3D, the gasied natural gas is divided into
two streams. The high pressure natural gas can be directly supplied to customers through one
stream, and the second stream of high pressure gas expands through gas turbine T2, producing
output work. The discharge low pressure gas condenses into liquid in heat exchanger E2A, and
the condensed liquid recirculates into the system after being increased in pressure through
pump P2. In fact, turbine T2, heat exchangers E2B and E3D, condenser E2A and pump P2
constitute one Rankine cycle using the natural gas as the working substance. The gas supplied

Fig. 5. Mixed cycle for LNG cold heat exergy application (low pressure case).
1524 H. Liu, L. You / Energy Conversion & Management 40 (1999) 15151525

Fig. 6. Mixed cycle for LNG cold heat exergy application (high pressure case).

to the customers in this system does not join in any expansion process, so it is more suitable
for the case when the required gas pressure is relatively high (such as 7 MPa).
From the preceding discussions, it can be seen that the mixed cycle may use the low
temperature exergy and pressure exergy simultaneously and may attain a high eciency for
recovering the cold heat of LNG. For example, a 450 MW LNG power plant consumes
approximately 150 t/h LNG. If the cold heat is recovered by the cycle in Fig. 5 for power
generation, the output power will attain 11700 kW. Considering long term operation, the
economic prot will be signicant. In fact, some power generating units using LNG cold heat
have been placed in commercial operation [7,8].
Besides power generation, the cold heat of LNG can be used to liquefy oxygen, nitrogen and
carbon dioxide and for cryogenic shattering, ultra low temperature warehouse and other low
temperature usages.

5. Conclusions

The exergy analysis method for both liquid and gaseous natural gas is presented in this
paper. To facilitate the analysis and determine which factor contributes most to the total
exergy of LNG, the total exergy is decomposed into temperature exergy and pressure exergy.
The inuences of various factors on the low temperature exergy, pressure exergy and total
exergy are discussed. The following conclusions can be drawn from the results of the analysis:

1. The cold heat exergy of LNG can be divided into the low temperature exergy and the
pressure exergy. Both of them increase with ambient temperature.
2. With increase of system pressure, the low temperature exergy of LNG decreases, the
pressure exergy increases, and the total cold heat exergy decreases. However, the decreasing
tendency is slower when P > 2 MPa.
3. The total of LNG cold heat exergy increases with methane concentration in the methane
ethane binary mixture.
4. The economic potential to use the LNG cold heat is signicant and various dierent
schemes, including several mixed cycles, can be used. When Ex,th  Ex,p , a low boiling
 H. Liu, L. You / Energy Conversion & Management 40 (1999) 15151525 1525

temperature Rankine cycle may be used; when Ex,p  Ex,th , a one stage or multistage
natural gas direct expansion cycle may be used; and when Ex,th Ex,p , mixed cycles may be
used. The best cycle must be determined by optimization of the thermodynamic cycle, the
required gas supply pressure and economics.
5. The exergy analysis method proposed in this paper may also be used in other low
temperature applications.

References

[1] You LX. Advances of cryogenics in aeronautics and astronautics. Journal of Nanjing University of Aeronautics
and Astronautics 1992;24(1):6980.
[2] Blomen LJM, Mugerwa MN. Fuel cell systems. New York: Plenum, 1993.
[3] Kotas TJ. The exergy method of thermal plant analysis. London: Butterworths, 1985.
[4] You LX, Gu AZ. Prediction of LNG densities using shape factor corresponding state principles. Journal of
Aeronautic Power 1992;7(3):2846.
[5] You LX, Gu AZ. An improved method for predicting VLE of LNG. In: Proc. LNG10, Malaysia. 1992. p. 24.
13.
[6] Walas SM. Phase equilibria in chemical engineering. London: ButterworthHeinemann, 1984.
[7] Shiozawa H, Hiro-oka T. Power generation using cold potential of LNG in multicomponent uid Rankine
cycle. Adv Cryog Eng 1981;27:9718.
[8] Sanga Y, Shirasaki Y. Control system of power generation plant from LNG cold heat. Adv Cryog Eng
1981;27:97990.