Reliquefaction

1759

Yajun Li
Guang Jin

Research Article

Zhiliang Zhong

Thermodynamic Analysis-Based Improvement

for the Boil-Off Gas Reliquefaction Process of
Liquefied Ethylene Vessels

South China University of

Technology, School of Chemistry
and Chemical Engineering,
Key Lab of Heat Transfer
Enhancement and Energy
Conservation of the Ministry of
Education, Guangzhou, China.

A new optimization design of the boil-off gas (BOG) reliquefaction process for
liquefied ethylene (LEG) vessels is proposed in order to reduce the reliquefaction
process energy cost and improve its cold exergy efficiency. The exergy loss of each
component is calculated and the efficiency of the available energy utilization is
evaluated on the basis of a detailed thermodynamic analysis. The exergy analysis
results indicate that the exergy efficiency of the improved BOG reliquefaction
process is about 19.0 % higher than that of the existing process, and the amount
of refrigerant used in the improved process is reduced by about 44.9 % per hour.
The power consumption could be decreased by 16 %. The circulation volumes of
the refrigerant and BOG are both significantly reduced, thus lowering the equipment and operation costs of the BOG reliquefaction process.
Keywords: Exergy efficiency, Liquefied ethylene, Refrigeration cycle, Reliquefaction
Received: January 09, 2012; revised: June 21, 2012; accepted: June 27, 2012
DOI: 10.1002/ceat.201200019

Introduction

The ethylene production capacity represents the scale and level

of the petrochemical industry in a country because of the great
importance of ethylene which is mostly converted into ethylene glycol and a variety of other derivatives. To address issues
related to Chinas finite ethylene resource and large quantities
of demand, alternative seaborne ethylene from foreign countries has been proposed. The consumption of ethylene in China is expected to exceed 38.95 million tons by 2015. In 2010,
the consumption of ethylene in China was 25 million tons,
while its self-production was only 14 million tons [1].
Liquefied ethylene (LEG) is a kind of cryogenic liquid that
boils at 169 K and a pressure of 0.1 MPa. The volume of liquefied ethylene is about 1/460 of that of its gaseous equivalent.
Therefore, ethylene in the liquid phase is the most cost-effective and flexible way for long-distance transportation around
the world. During the transportation, a portion of the LEG will
be vaporized by heat that penetrates in the cargo containment
system. Although the cargo tanks are well insulated, some
boil-off gas (BOG) is still inevitably going to be produced by

Correspondence: Prof. Y. Li (liyajun@scut.edu.cn), South China University of Technology, School of Chemistry and Chemical Engineering,
Key Lab of Heat Transfer Enhancement and Energy Conservation of
the Ministry of Education, Guangzhou 510640, Guangdong Province,
China.

Chem. Eng. Technol. 2012, 35, No. 10, 17591764

heat leakage. The nominal boil-off ratio is about 0.20.38 % of

the tank capacity per day [2]. One disadvantage is that the
BOG of LEG can cause excessive buildup of pressure and temperature in LEG tanks. High pressure in the tank may destroy
the structure of the cargo tank and bring about serious safety
problems [3]. Evidently, venting BOG without energy recovery
is not economical since more than 0.1 % of LEG in the cargo
tanks evaporates every day. As a result, a reliquefaction plant is
usually installed to provide sufficient cooling capacity in order
to maintain the pressure and temperature in the cargo tank
within a safe range.
At present, there exist only a few comprehensive reports on
the reliquefaction process for some liquefied petroleum gas
products or natural gas. Miliajev [4] presented results about
reliquefaction of propane and butane. Pil [5] investigated reliquefaction plants for liquefied natural gas (LNG) ships which
consist of separate reliquefaction and refrigeration units utilizing nitrogen (N2) as refrigerant, and assessed its reliability.
Moon [6] investigated the effects of various parameters on the
boil-off natural gas reliquefaction system performance. Remeljej [7] studied the performance of small-scale LNG liquefaction processes based on exergy analysis. However, few studies
are dedicated to ethylene.
In this paper, a cost-effective optimization design of the
BOG reliquefaction process for LEG vessels is proposed. The
performance of the reliquefaction system and refrigeration
cycle was investigated based on the exergy analysis, and the
performance of the improvement process was compared with
that of the existing process.

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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1760

Y. Li et al.

Existing BOG Reliquefaction Process

2.1

Process Description

condenser E1, where it is condensed to 235 K by the refrigerant

R404A. Then the condensed ethylene is split. One stream at a
rate of 645 kg h1 is throttled by throttle valve TV2 and directed to the intermediate cooler E2 to cool another stream
(2955 kg h1). The cooled ethylene is throttled by throttle valve
TV1 and then flows into the LEG tank. In the refrigeration
cycle, the working fluid R404A is compressed from 0.13 to
1.67 MPa by the two-stage compressors C3 and C4. After cooling by seawater, the cooled refrigerant is split into two streams.
One stream at a rate of 9110 kg h1 undergoes an isenthalpic
throttling expansion through throttle valve TV3 and is warmed
by the other stream (8986 kg h1). The cooled refrigerant
R404A flows through throttle valve TV4 and then enters the
ethylene condenser E1 to cool the BOG. The warmed refrigerant is recompressed by C3 and C4, thereby completing the
refrigerant cycle.
The amount of refrigerant used in the existing BOG reliquefaction process is 18 096 kg h1. Compressors are the
main power consumption equipment, and the total actual
power consumption of the compressors in the process is
629.0 kW.

Fig. 1 presents a schematic diagram of the existing BOG reliquefaction process of the LEG vessel which was manufactured
in China for a Norwegian buyer. This LEG vessel contains two
insulated cargo tanks with a total capacity of 10 000 m3. The
cargo tank is designed for working under pressures in the
range from 0.11 to 0.12 MPa and operating at 171 K. During
transportation, the rate of LEG vaporization would be approximately 0.3 % per day by heat transferred from the surroundings. Given the terms above, the reliquefaction plant is
designed for liquefying BOG at a rate of 2955 kg h1 to maintain the tank pressure stable and keep the temperature changing between 171 and 175 K within 90 h.
The BOG reliquefaction process consists of a reliquefaction
cycle and a refrigeration cycle. In the reliquefaction cycle, the
0.11 MPa BOG from the LEG tank is compressed to 1.72 MPa
by the two-stage compressors C1 and C2 and then cooled
down by seawater. Afterward, the BOG enters the ethylene

H=47 S=3.4
T=305

H=47 S=3.47
T=231.8

H=218 S=3.95
T=342 P=1.67

W2

H=-49 S=3.05
T=235

TV3

E3

M
H=-49 S=3.05
T=231.5

C4

H=179 S=3.92
T=286 P=0.49

C3
H=142 S=3.88
T=232.3 P=0.13

H=146 S=4.77
T=203.1

M2
TV4
H=331 S=6.67
T=305

E1
W1
E2

H=418 S=6.93
T=352 P=1.72

TV2
H=-146 S=4.73
T=235

M
C2

H=195 S=6.44
T=203.2

Units:
Enthalpy H: kJkg-1
Entropy S: kJK-1kg-1
Temperature T: K
Pressure P MPa

H=-220 S=4.4
T=207

TV1

C1
M1
H=295 S=6.87
T=270 P=0.52

H=169 S=6.73
T=171 P=0.11

H=-220 S=4.46
T=171

Ethylene tank

Figure 1. Schematic of the existing ethylene BOG reliquefaction process. TV1, TV2, TV3, TV4: throttle valves; E: ethylene condenser; E2,
E3: intermediate coolers; C1, C2, C3, C4: compressors; W1, W2: seawater heat exchangers; M1, M2: blenders.

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Chem. Eng. Technol. 2012, 35, No. 10, 17591764

Reliquefaction

2.2 Thermodynamic Process Analysis

Usually, according to the first law of thermodynamics, the
coefficient of performance (COP) is applied to evaluate the
thermal characteristics of a refrigeration cycle, and defined as
the amount of cooling capacity produced by per unit work [8].
COP represents the quantity of energy being used. However, it
cannot disclose the level of energy quality. The dimensionless
correlations of energy in each energy conversion step can be
expressed by the exergy, which also can easily differentiate between quantity and quality of energy loss in each part of the
process.

1761

various operations, such as heat exchange, compression,

blending, and throttling, the expressions of exergy loss [18] are
defined as follows:
For compressor:
II Hout

Hin 1=ga

1 T0 Sout

Sin

(1)

For blender:
II T0 Sout

Sin2

(2)

For countercurrent-flow heat exchanger:

X
X
X
X 
II
Ein
Sout
Eout T0
Sin

(3)

Sin1

2.2.1 Exergy Analysis Modeling

For seawater heat exchanger:
Exergy analysis is a powerful tool in design, optimization, and
Q
T
performance evaluation of an energy system. Its principles and
ln wout
(4)
II T0 Sout Sin T0
methodologies are well-established [913]. Exergy analysis
DT
Twin
usually aims at supporting the goal of more available energy
use by assessing the significant efficiencies and by enabling the
For throttle valve:
locations, types, and true magnitudes of energy wastes and
losses [1417]. Since the reliquefaction of BOG is the most en(5)
II T0 Sout Sin
ergy-demanding process, exergy analysis is essential to optimize the design of the reliquefaction process. Exergy analysis
where Hin and Hout are the individual enthalpies of the workin the system for each component indicates how the input
ing fluid at the inlet and outlet of each component; Sin and Sout
exergy provided by the compressor is destroyed when the
are the individual entropies of the working fluid at the inlet
working fluid goes through its cycle, and hence, it suggests a
and outlet of each component; ga is the efficiency of the comdirection for process improvement and optimization.
pressor; Q is the heat load of the heat exchanger; DT is the
Energy and exergy analysis is used to evaluate the efficiency
temperature change of seawater; Twin and Twout are the indiof the consumed available energy. The exergy loss of each comvidual temperatures of seawater at the inlet and outlet of the
ponent is calculated on the basis of enthalpy and entropy. The
heat exchanger; T0 is the ambient temperature.
values of enthalpy and entropy are obtained by calculation.
Here, they are determined by the commercial chemical engineering process program PRO/II which calculates the states
2.2.2 Exergy Analysis
from steady-state heat and mass balances and the performance
data for the equipments. In agreement with the model, the refBased on the equations described above, the calculation results
erence conditions are set at 298 K and 0.101 MPa. It should be
of exergy loss of each component are presented in Tab. 1. The
noted that the total exergy input
from the outside system means
Table 1. Exergy analysis results of the existing BOG reliquefaction process.
that the exergy input from the
Refrigeration cycle
Reliquefaction cycle
compressors and the exergy loss
exist in a series of energy conversaAmount
Percentage
Amount
Percentage
tion steps.
[kW]
[%]
[kW]
[%]
Because most of the work input
Exergy input
Compressor
384.8
100
244.2
71.1
of the seawater pump is transformed into the seawater flow exReliquefaction

99.3
28.9
ergy, the seawater leaves the two
Exergy loss
Compressor
112.3
29.2
72.9
21.2
cycles after exchanging heat with
Seawater heat exchanger
40.9
10.6
8.0
2.4
the compressed BOG or refrigerant, therefore, the work input and
Ethylene condenser
36.7
9.5

the exergy loss of the seawater

Throttle valve
52.2
13.6
17.4
5.1
pump are not considered here for
exergy analysis of the BOG reliqueCooler
43.1
11.2
7.3
2.1
faction process. The system, illusBlender
0.3
0.1
2.5
0.7
trated in Fig. 1, includes compressors, blenders, countercurrent-flow
Total
285.5
74.2
108.1
31.5
heat exchangers, seawater heat exCold exergy
99.3
25.8
235.4
68.5
changers, and throttle valves. For

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1762

Y. Li et al.

the return gas refrigerant and the cryogenic BOG is beneficial

to improve the energy utilization efficiency of the whole process. Based on this analysis, for the improved process coldboxes are added, cold energy of the return gas refrigerant is
used to cool the high-pressure refrigerant in Cold-box 2, and
the cryogenic BOG is taken to cool the high-pressure LEG
from the ethylene condenser by Cold-box 1.

exergy losses of compressor, seawater heat exchanger, and

throttle valve expressed here are the sum of exergy losses of
those facilities in each cycle. In the refrigeration cycle, the cold
exergy provided to the BOG reliquefaction cycle by cryogen is
the difference between exergy input of compressor and total
exergy loss. In the ethylene BOG reliquefaction cycle, the cold
exergy obtained by BOG is the exergy input of the compressor
plus the cold exergy from the refrigeration cycle, minus the
total exergy loss.
Tab. 1 illustrates that in both the refrigeration cycle and reliquefaction cycle of the existing BOG reliquefaction process,
the compressor is the unit with the maximal exergy loss, i.e.,
29.2 % and 21.2 %, respectively. The main reason for this high
exergy loss is that the compression process deviates far from
an isentropic process. Therefore, the choice of a compressor
with high performance can enhance the compression efficiency
and reduce exergy loss. The throttle valve and cooler have the
second highest exergy loss. The liquid passing through the
throttle valve usually becomes the liquid-vapor blended phase,
so the lower inlet temperature before throttling can reduce the
vapor portion and ensure the throttle valve to perform stably,
and less vapor means less depletion of refrigerant. Thereby, it
is more cost-effective. Since the reliquefaction of BOG is the
most energy-demanding process, recycling the cold energy of

Improved BOG Reliquefaction Process

3.1

Process Description

Fig. 2 presents a schematic diagram of the improved BOG reliquefaction process [19]. The high-pressure refrigerant from
the compressor is cooled in Cold-box 2 by cold energy of the
232 K return refrigerant gas. Then the high pressure refrigerant
is split into two streams. One stream at a rate of 2609 kg h1
undergoes an isenthalpic throttling expansion through throttle
valve TV3 and is warmed by the other stream at a rate of
7369 kg h1. In the BOG reliquefaction cycle, the BOG with a
temperature of 171 K, vaporized from the LEG tank, is used to
cool the high-pressure LEG from the ethylene condenser E1 in
Cold-box 1. It decreases the cooling load of the ethylene conH=240 S=4.01
T=362 P=1.67

H=0.68 S=3.27
T=232

W2

H=236 S=4.1
T=346 P=0.49

H=0.68 S=3.24
T=273
M
E3

TV3

H=-49 S=3.05
T=235

H=142 S=3.88
T=232.3

C3

C4
W3
H=47 S=3.4
T=305

TV4
H=-49 S=3.05
T=231.5

M2

Cold-box 2
H=331 S=6.67
T=305

E1
H=412 S=7.26
T= 341 P=0.52
H=-146 S=4.73
T=235

H=188 S=4.06
T=289 P=0.13

W1

W4

H=520 S=7.2
T=405 P=1.72

M
C2

C1
H=244 S=7.1
T=227 P=0.11

Units:
Enthalpy H: kJkg-1
Entropy S: kJK-1kg-1
Temperature T: K
Pressure P MPa

Cold-box 1

TV1

H=169 S=6.732
T=171

H=-220 S=4.4
T=207
H=-220 S=4.46
T=171

Ethylene tank

Figure 2. Schematic of the improved ethylene BOG reliquefaction process. TV1, TV3, TV4: throttle valves; E1: ethylene condenser; E3: intermediate cooler; C1, C2, C3, C4: compressors; W1, W2, W3, W4: seawater heat exchangers; M2: blender.

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Reliquefaction

1763

denser and reduces the refrigerant used in the refrigeration

cycle. In addition, for the cold energy of the low-temperature
BOG is used, the ethylene from the ethylene condenser does
not need to be throttled, and the energy utilization efficiency
of the whole process is improved.
In the improved process, two cold-boxes are added. The
heat loads of Cold-box 1 and Cold-box 2 are 5.2 104 and
11.03 104 kcal h1, respectively. The areas of Cold-box 1 and
Cold-box 2 are estimated as 25 and 31 m2. So, the cost of the
two cold-boxes is low. In addition, by recycling the cold energy
of the BOG and refrigerant by adding two cold-boxes, the
amount of refrigerant used in the improved process is
9978 kg h1, reduced by about 44.8 %. The diameter of the
refrigeration cycle tube is 0.65 times smaller than that of the
existing process. Moreover, the cooler E2 and throttle valve
TV2 are removed. These facts lead to the simultaneous reduction of the equipment and operation costs of the BOG reliquefaction process. The energy utilization efficiency of the whole
process is improved. As indicated in Tab. 2, the total work consumption of the improved process decreases 100.6 kW power,
by 16 %. The COP value is calculated to be 0.604 for the improved process, which is increased by 18.9 %.

Table 2. Energy consumption comparison between the existing

and the improved process.

3.2

Exergy Analysis of the Improved Process and

Result Comparison

Compression
ratio

Existing
process

Improved
process

C1

4.7

103.7

138.4

C2

3.3

140.5

137.8

C3

3.8

189.1

133.6

C4

3.4

195.7

118.6

Total work consumption W [kW]

629

528.4

Refrigeration capacity q [kW]

319.3

319.3

Parameter

Work of
compressor
[kW]

COP

0.508

0.604

q
Coefficient of performance: COP =
W

the BOG reliquefaction system, WC is the power input of the

compressor of the whole system. Therefore, the exergy efficiency of the improved BOG reliquefaction process is 44.5 %, i.e.,
about 19.0 % higher than that of the existing process (37.4 %).

Conclusions

A cost-effective optimization design is carried out to utilize

cold energy, which consists of the low-temperature refrigerant
The calculated exergy loss results of each component of the
return gas and the low-temperature BOG vaporized from the
improved process are presented in Tab. 3. The refrigerant and
LEG tank, by the two cold-boxes in the current BOG reliqueLEG temperatures before throttling decrease when the coldfaction process. Due to the cold energy recovery of the lowboxes are added, the performances of throttle valve and cooler
temperature BOG and recycle refrigeration in the improved
are improved. The exergy loss percentage of the throttle valve
process, the amount of refrigerant used in the improved prodecreases from 13.6 to 3.3 % in the refrigeration cycle and that
cess is reduced by about 44.8 %. Compared with the existing
of the cooler from 11.2 to 4.6 %.
process, the improved version saves 100.6 kW power consumpExergy efficiency, defined as the amount of cold exergy protion (16 %). The exergy analysis results demonstrate that the
duced per unit work, is used to evaluate the thermal characteristics of the refrigeration cycle
instead of COP. The calculated exTable 3. Exergy analysis results of the improved BOG reliquefaction process.
ergy efficiencies of the improved
and the existing refrigeration cycle
Refrigeration cycle
Reliquefaction cycle
are 32.3 % and 25.8 %, respectively.
Amount
Percentage
Amount
Percentage
The exergy efficiency of the refrig[kW]
[%]
[kW]
[%]
eration cycle is increased by about
25.2 %. The total compression
Exergy input
Compressor
252.2
100
276.2
77.2
work inputs to the existing and the
Reliquefaction

81.5
22.8
improved process are 629.0 and
528.4 kW, respectively, and the toExergy loss
Compressor
74.2
29.4
73.2
20.5
tal cold exergy provided to the exSeawater heat exchanger
31.7
12.6
24.3
6.8
isting and the improved reliquefacEthylene condenser
30.1
12.0

tion system is 235.4 kW. According

to the exergy analysis of both proThrottle valve
8.4
3.3
15.4
4.3
cesses, the exergy efficiencies of the
Cooler
11.5
4.6

entire BOG reliquefaction process

WBOG
Blender
0.1
0.02

derived from equation g

WC
Cold box
14.7
5.8
9.4
2.6
are 0.374 and 0.445, respectively.
Here, WBOG is the power conTotal
170.7
67.7
122.3
34.2
sumed by BOG reliquefaction,
Cold exergy
81.5
32.3
235.4
65.8
which is equal to the cold exergy of

Chem. Eng. Technol. 2012, 35, No. 10, 17591764

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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1764

Y. Li et al.

exergy efficiency of the improved refrigeration cycle is increased by 25.2 % compared with that of the existing process.
The cold exergy efficiency of the improved BOG reliquefaction
process is 44.5 %, about 19.0 % higher than that of the existing
process with 37.4 %, and the available energy utilization efficiency of the BOG reliquefaction process is improved.
The authors have declared no conflict of interest.

Symbols used
H
Q
S
T
T0
DT
Q
WBOG

[kJ kg1]
[kJ]
[kJ kg1K1]
[K]
[K]
[K]
[kJ]
[kW]

WC
g
ga

[kW]
[]
[]

enthalpy
heat load of heat exchanger
entropy
temperature
ambient temperature
seawater temperature changed
heat load of heat exchanger
power consumed by
reliquefaction
power input of compressor
exergy efficiency
efficiency of compressor

Subscripts
in
out
c
w

inlet of each component

outlet of each component
compressor
water

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Chem. Eng. Technol. 2012, 35, No. 10, 17591764