Energy 42 (2012) 522e529

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Energy
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A novel CO2 cryogenic liquefaction and separation system

Gang Xu, Le Li, Yongping Yang*, Longhu Tian, Tong Liu, Kai Zhang
Key Laboratory of Condition Monitoring and Control for Power Plant Equipment of Ministry of Education, School of Energy Power and Mechanical Engineering,
North China Electric Power University, Beijing 102206, China

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, the phase transition characteristics of CO2 and CO2/H2 mixture are analyzed, and ideas for
Received 20 August 2011 improving the cryogenic separation method are drawn. On this basis, a novel CO2 cryogenic liquefaction
Received in revised form and separation system is put forward. In the novel system, two-stage compression, two-stage refriger-
19 February 2012
ation, two-stage separation, and sufficient recovery of cryogenic energy are adopted. Two-stage
Accepted 21 February 2012
Available online 14 April 2012
compression can increase the total pressure of gas mixture and liquefaction temperature of CO2. Two-
stage refrigeration and two-stage separation can reduce the cryogenic energy demand and compres-
sion work in subsequent steps. Sufficient recovery of the cryogenic energy can reduce refrigeration
Keywords:
CO2 liquefaction and separation
duties. All these measures decrease the total energy consumption. As a result, under a CO2 recovery ratio
Cryogenic energy of 90%, the total energy consumption is only 0.395 MJ/kgCO2 with over 99% CO2 purity. Further analysis
Two-stage stages separation indicates that the proposed CO2 cryogenic liquefaction and separation system is more suitable for
Low energy penalty separating liquid CO2 from gas mixtures with high CO2 concentration, and that the high initial pressure of
the mixture presents better performance. The proposed system can serve as a new approach to CO2
removal with low energy penalty.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
The use of fossil fuels represents the largest source of carbon
dioxide (CO2) emissions, a significant greenhouse gas that is largely
blamed for global warming [1,2]. In the foreseeable future,
however, fossil fuels are still expected to play a dominant role in
energy production [2e4]. Thus, realizing CO2 reduction in fossil fuel
utilization is a daunting challenge and an urgent task in science
research and technology development [1,3e5].
CO2 capture and storage is a technically feasible method for the
substantial reduction of CO2 emissions from fossil energy utiliza-
tion systems [1,6,7]. Four primary approaches aimed at CO2 sepa-
ration from flue gas are currently available: absorption (including
chemical and physical absorption), adsorption, the use of
membranes, and cryogenic processes [1,8]. Among them, chemical
absorption (e.g., amine and hot aqueous K2CO3 solution) is effective
for dilute CO2 streams, such as coal combustion flue gases, which
typically contain only about 10%e15% CO2 by volume [7e9]. From
the perspective of energy consumption, physical absorption (e.g.,
Selexol solvent) is typically used for CO2 removal from syngas
before combustion because it exhibits good absorption property at
* Corresponding author. Tel./fax: þ86 10 61772011.
E-mail address: yyp@ncepu.edu.cn (Y. Yang).
high pressure [1,10]. Both these absorption methods have drawn
considerable attention and have been applied in some demon-
stration projects because of their relatively high maturity and
feasibility for large-scale utilization; however, these methods
continue to present certain difficulties such as the stability of the
solvents and the huge energy requirements for stripping CO2 from
the loaded solvent [10e12]. The adsorption and membrane
processes are also recognized as promising CO2 capture methods
because of their potential to lower energy consumption in CO2
separation, although problems, such as limited scale and low CO2
purity, still exist [1,12e16].
CO2 capture with cryogenic energy is a unique separation
method. Under the cryogenic separation process, the components
of a mixture can be separated by a series of compression, cooling,
and expansion steps, carried out on the basis of the differences
among the phase transition properties of these components [1].
Some scholars continue to devote their efforts to research on this
method and have accomplished many valuable results [17e23]. For
example, Zhang et al. studied a liquefied natural gas-fueled quasi-
combined power plant using supercritical CO2 Rankine-like and
Brayton cycles [17e19]. Zanganeh et al. introduced and discussed
the challenges, development stages, and commissioning of a pilot-
scale CO2 capture and compression unit, which can separate CO2 as
liquid phase from the flue gas of oxy-fuel combustion [20]. Amann
et al. evaluated the technical performance of a natural gas

0360-5442/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.energy.2012.02.048
 G. Xu et al. / Energy 42 (2012) 522e529 523

combined cycle converted for oxy-fuel combustion using O2/CO2 10000

cycle with a cryogenic CO2 recovery process [21]. Tuinier et al.
designed a novel heat exchange device, called a dynamically
operated packed bed, in which effective separation on the basis of 1000
differences in dew and sublimation points can be achieved without
increasing pressure drops or plugging problems [22]. Hart et al. liquid
critical point

Pressure (bar)
developed a cryogenic CO2 separation process, in which CO2 is 100 solid
cooled into a three-phase mixture and the solid CO2 is melted by
a heater, and then separated with the liquid [23].
These studies reveal the unique advantages of CO2 recovery 10
using cryogenic energy: (1) Liquid CO2 is directly produced at
triple point
a relatively low pressure, avoiding huge energy consumption in
compressing gaseous CO2 to a very high pressure [17e21,23]; and 1 gas
(2) the cryogenic separation method is based on relatively mature
industrial processes, such as compression and refrigeration, indi-
cating easy expansion to industrial-scale utilization [17e23]. 0.1
However, to achieve CO2 condensation, the mixture requires -100 -90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80
o
reduction to a very low-temperature, which causes the following Temperature ( C)
problems: (1) substantial energy consumption for refrigeration,
leading to high energy penalty for CO2 capture [17e23], and (2) Fig. 1. Three-phase diagram of CO2.

CO2 solidification under a low-temperature, which causes several

operational problems, such as the blockage of pipes or heaters
[17e19,22,23]. Therefore, the key point in improving the cryogenic
method lies in how to achieve CO2 liquefaction at a relatively high
temperature.
In our previous work [6], we proposed a novel coal-based
hydrogen production system, which can elevate the CO2 concen-
tration of the gas mixture that enters the capture process, avoid CO2
solidification during the cryogenic recovery process, and
lower energy consumption in CO2 capture, through the effective
integration of hydrogen production and CO2 cryogenic capture
processes.
On this basis, the present paper further discusses integration
and optimization within a CO2 cryogenic capture system to reduce
the energy penalty for cryogenic CO2 capture. This study aims to (1)
study the phase transition characteristics of CO2/H2 mixture to
explore the possibility of improving the performance of the cryo-
genic separation of CO2; (2) introduce a new idea for the integration
of two-stage compression, two-stage refrigeration, and two-stage
separation to decrease energy consumption in CO2 compression
and refrigeration; and (3) propose a novel CO2 cryogenic liquefac-
tion and separation method for capturing CO2 with low energy
penalty.
in the mixture is increased to 80%, 90% CO2 can be separated from
the gas mixture at a temperature of 48  C. Such temperature is
above the triple point of CO2, resulting in no CO2 solidification. In
addition, cryogenic energy within the range 0 to 48  C can be
obtained more easily than cryogenic energy below 48  C, which
can be produced by more complicated refrigeration cycles with
lower coefficient of performance (COP). Thus, enhancing CO2
concentration is helpful in lowering energy consumption in
refrigeration.
Therefore, the analysis above provides an important approach to
improving the cryogenic separation method. That is, increasing CO2
concentration in the mixture to 80% or higher before initiating the
separation process prevents CO2 solidification and decreases
cryogenic energy consumption. Effectively increasing CO2 concen-
tration in the gas mixture significantly improves the performance
of the cryogenic separation method.
An effective approach to increasing the concentration of CO2 in
the gas mixture is system integration. For example, when a gas
mixture mainly composed of H2 and CO2 is incorporated into
a clean fuel production process, more H2 is consumed to produce
hydrogen-rich clean fuel. Meanwhile, the concentration of CO2 in

2. Proposed cryogenic liquefaction and separation system

2.1. Improvement ideas for the cryogenic separation method

Pressure of CO2/H2 Mixture is 30 bar
Fig. 1 shows the three-phase diagram of CO2. The liquefaction 100%
temperature of CO2 is determined mainly by its pressure. The
90%
increase in CO2 pressure enhances its liquefaction temperature,
CO2 Separation Rate

80%
which can lower energy consumption in refrigeration and prevent
70%
equipment from freezing. Thus, the increase in CO2 pressure can be
a noteworthy improvement idea for the cryogenic separation 60%

method. 50% CO2 concentration

In general, two factors can directly affect the CO2 pressure in 40% A: 80%
a gas mixture: one is CO2 concentration, and the other is the total B: 60%
30%
pressure of the gas mixture. A B C C: 40%
20%
10%
2.1.1. Influence of initial CO2 concentration
Fig. 2 shows the characteristics of the temperature drop in CO2/ 0 -20 -40 -60 -80 -100
H2 mixture at different CO2 concentrations. Under a pressure of o
Temperature of Gas Mixture ( C)
30 bar and at CO2 concentrations of 40% and 60%, the temperature
must be reduced to about 81 and 66  C, respectively, to separate Fig. 2. Variation in CO2 concentration and separation ratio of CO2/H2 mixture with
90% CO2 from the gas mixture. However, when CO2 concentration temperature.
524 G. Xu et al. / Energy 42 (2012) 522e529
CO2 Concentration of CO2 /H2 Mixture is 80%
100%
90%
80%
CO2 Separation Ratio
70%
60%
The Pressure of CO2 / H2
50%
40%
Mixture
A: 60 bar
30%
A B B: 30 bar
20% C C: 15 bar
C: 15 bar
10%
0 -20 -40 -60 -80 -100
o
Temperature of Gas Mixture ( C)
Fig. 3. Variation in pressure and separation ratio of CO2/H2 mixture with temperature.
H2/CO2 mixture can be markedly increased. In our previous study,
we put forward a coal-based hydrogen production system with low
CO2 emission using the aforementioned idea as basis [6]. In the
system, the performance of CO2 cryogenic separation considerably
improves because of the increase in CO2 concentration; this
increase in concentration results from the system integration of
clean fuel production and cryogenic CO2 separation.
2.1.2. Influence of gas mixture pressure
Fig. 3 shows the relationship between CO2 separation ratio and
the temperature of CO2/N2 mixture under different pressures, at
a CO2 concentration of 80%. Under the mixture pressures of 15, 30,
and 60 bar, the temperature should be lowered to about 63, 48,
and 30  C, respectively, to separate 90% CO2 from the mixture. In
other words, enhancing the mixture pressure can also effectively
increase the separation temperature of CO2, thereby improving the
performance of the CO2 cryogenic method.
After the gas mixture enters the cryogenic CO2 separation unit,
the CO2 concentration in the gas mixture continuously declines
with CO2 condensation. If the total pressure of the gas mixture is
kept unchanged, the partial pressure and liquefaction temperature
of CO2 will decrease along with the reduction in its concentration;
this phenomenon may impose a negative influence on the perfor-
mance of the cryogenic separation method. Therefore, increasing
the total pressure of the gas mixture is also an essential approach to
maintaining the liquefaction temperature of CO2 at a relatively high
level during CO2 cryogenic separation.
However, if the concentration of CO2 in the gas mixture is very
low, the increase in CO2 liquefaction temperature will be con-
strained by the enhancement of gas mixture pressure. As is shown
in Fig. 4, when the concentration of CO2 is only 15%, the temper-
ature should be reduced to 82  C to separate 80% CO2 from the
gas mixture even if the total pressure of the mixture increases to
60 bar. Thus, enhancing the pressure of the gas mixture is another
effective approach to improving the performance of cryogenic
separation, but only at a sufficiently high CO2 concentration in the
gas mixture.
Figs. 2e4 are simulated and calculated through Peng-Robinson
Equation. The prediction of Peng-Robinson Equation can reflect
the phase equilibria of mixture system, especially to nonpolar gas
system. And CO2 and H2 are both two kinds of typical nonpolar
gases. So Peng-Robinson Equation can deal with CO2/H2 mixture
system satisfactorily. And the prediction of Peng-Robinson equa-
tion behaves better in matching the experimental dates CO2/H2
mixture in lower pressure [24].
CO2 /H2 Gas Mixture with CO2 Concentration of 15%
100%
90%
CO2 Separation Ratio
80%
70%
60% The Pressure of CO2 / H2 Mixture
50% A: 60 bar
40% B: 30 bar
30%
20%
A B C
10%
0 -20 -40 -60 -80 -100
o
Temperature of Gas Mixture ( C)
Fig. 4. Variation in pressure and separation ratio of CO2/H2 mixture with temperature
at 15% CO2 concentration.
2.2. Novel CO2 cryogenic liquefaction and separation system
Based on the First Law of Thermodynamics (Energy Conserva-
tion), and the Second Law of Thermodynamics (Energy Cascade
Utilization), and combined with the phase transition properties
analysis above, a novel CO2 cryogenic liquefaction and separation
system is proposed. The system is an improved cryogenic separa-
tion process with two-stage compression, refrigeration, and gas-
liquid separation to keep the CO2 liquefaction temperatures at
a relatively high level, as well as achieve a satisfactory CO2 recovery
ratio (the ratio of recovered CO2 to the total amount of CO2 in the
original mixture) and a relatively low energy penalty.
The conceptual configuration of the novel cryogenic CO2 lique-
faction and separation system is shown in Fig. 5. The system is
composed of two cascading steps with similar constructions and
functions. Each step includes one compressor, two heat exchangers,
one separator, and one liquid pump. In Step 1, the gas mixture (S1) is
compressed to a suitable pressure by C1 (S2), and then refrigerated
to a low-temperature after passing through heat exchangers H1 and
H2 to condense some of the CO2 as liquid. The condensed CO2 is
separated in separator Sep1 as liquid (S5) and then enters H1 for the
recovery of its cryogenic energy (S6). The remaining gas mixture (S4)
then sequentially enters Steps 2 to liquefy excess CO2 (S9), liquid CO2
(S9) provides cold duties to H3 (S10), after which it is mixed with the
liquid CO2 (S6) and flow out of the system (S15). After the two steps
of refrigeration and separation are completed, the remaining H2-rich
purge gas (S11) also enters heat exchanger H3 for the recovery of its
cryogenic energy (S12). Before discharge, it is heated in H5 by the
heat released by compressor C1 (S13), and expands to a suitable
pressure in the expansion turbine (T) for subsequent use (S14).
On the whole, the novel CO2 cryogenic separation system has
the following features: (1) Two-stage compression of gas mixture is
adopted, which can increase the pressure of the gas mixture during
the separation process and keep the partial pressure and liquefac-
tion temperature of CO2 at a relatively high level, although the
concentration of CO2 in the mixture declines with the liquefaction
of CO2. (2) The cryogenic energy of the products is fully recovered in
the process. For example, the purge gas and liquid CO2 are recycled
to provide considerable cold duties to refrigerate CO2/H2 mixture
before it flows out of the system. (3) Finally, two-stage separation is
applied in the system, through which liquefied CO2 can be sepa-
rated from the mixture in a timely manner to reduce cryogenic
energy and compression work demands in the subsequent step.
 G. Xu et al. / Energy 42 (2012) 522e529 525

Fig. 5. Novel CO2 cryogenic liquefaction and separation system.

3. Performance analysis of the novel system partial pressure of CO2 at a relatively high level (S7) given that its
CO2 concentration has been lowered because of the partial sepa-
3.1. Case description and simulation ration in Sep1. Then, the mixture is further cooled at 36  C after
being cooled through H3 and H4 and separated through Sep2. This
A gas mixture composed of 80% CO2 and 20% H2 was chosen for way, 27.4% (the recovery ratio of Step 1) of CO2 is further separated
the analysis of the performance of the novel CO2 cryogenic sepa- as liquid from the gas mixture (S9).
ration system. This kind of gas mixture can be found in many fuel After full recovery of cold duties, the two flows of liquid CO2 (S6
conversion processes. For example, in a coal-based hydrogen and S10) are mixed and sent out of the system (S15). The total
production process, after coal gasification and water-gas shift amount of the separated liquid CO2 (S15) can account for nearly 90%
reaction, the CO2 and H2 concentrations in the shifted gas are about of the CO2 in the original gas mixture (S1). In addition, the purity of
40% and 60%, respectively. When the shifted gas passes through the separated liquid CO2 (S20) can reach 99.33%.
a PSA hydrogen production process, the concentration of CO2 in the
remaining purge gas can be as high as about 70%e85%, with 70%e 3.2. Assessment of the thermodynamic properties
90% of H2 extracted [6]. In fact, cryogenic separation is also suitable
for mixtures of various compositions, such as N2/CO2, O2/CO2, Ar/ The summary of the thermodynamic properties of the novel CO2
CO2 or N2/O2/Ar/CO2, which will be discussed in our next paper. cryogenic separation process is given in Table 2, which shows that
Simulations were conducted using ASPEN PLUS. The thermody- the novel integrated process has a satisfactory comprehensive
namic properties of the mixtures were calculated using the Peng- performance. Its CO2 recovery ratio can reach 90%, and the energy
Robinson equation. The efficiency of the compressors and pumps penalty for the CO2 recovery unit can be as low as 0.395 MJ/kgCO2,
was assumed to be 0.8. The minimum temperature difference of the which is less than those of the MEA absorption (1.30 MJ/kgCO2) [28]
low-temperature heat exchanger is higher than 2  C. The cryogenic and Selexol absorption (0.53MJ/kgCO2) CO2 recovery processes
energy in the novel CO2 cryogenic liquefaction and separation [29]. It should be mentioned that, the comparison just shows that
system is from the vapor compression refrigeration system. R502 is the novel cryogenic separation system can achieve a satisfying
chosen to be the refrigerant, which is usually used in most low- performance with high initial CO2 concentration, not means that it
temperature conditions and has acceptable thermodynamics
Table 1
performance. Azeotropic mixture refrigerant R502 has the nearly Parameters of the main points of the new CO2 cryogenic liquefaction and separation
constant evaporation temperature [25e27]. In addition, the system.
temperature difference between the lowest mixture temperature
Flow Temperature Pressure Mass flow Mole Frac (%)
and refrigeration evaporation temperature will be 2  C or more. ( C) (bar) (kg/s)
The pressure, temperature, mole flow, and composition of the CO2 H2
main streams corresponding to the points shown in Fig. 5 are listed S1 35.0 5 100.0 80.00% 20.00%
in Table 1. As shown in the table, the pressure of the original gas S2 35.0 21 100.0 80.00% 20.00%
S3 25.0 21 100.0 80.00% 20.00%
mixture (S1) is only 5 bar. If the gas mixture is refrigerated under S4 35.6 21 38.0 60.06% 39.94%
this pressure, its temperature should drop to as low as 80  C to S5 31.7 21 62.0 99.69% 0.31%
start the separation of CO2 as solid state. However, if the flue gas is S6 14.4 80 62.0 99.69% 0.31%
compressed to 21 bar in the compressor (C1), 62.7% (the recovery S7 38.6 50 38.0 60.06% 39.94%
S8 13.5 50 38.0 60.06% 39.94%
ratio of Step 1) of CO2 (S5) will be condensed as liquid at 36.0  C
S9 30.6 50 27.1 98.52% 1.48%
after passing through H1 and H2, avoiding solid CO2 formation and S10 9.0 80 27.1 98.52% 1.48%
excessive energy consumption in deep refrigeration. After the S11 36.0 50 10.9 28.82% 71.18%
separation of liquid CO2 in Sep1, the CO2 concentration in the S12 27.0 50 10.9 28.82% 71.18%
mixture (S4) is reduced to 60.06%. S13 82.0 50 10.9 28.82% 71.18%
S14 16.1 20 10.9 28.82% 71.18%
Likewise, in the second step, the gas mixture (S4) should be S15 12.7 80 89.1 99.33% 0.67%
compressed to 50 bar through compressor (C2) to maintain the
526 G. Xu et al. / Energy 42 (2012) 522e529

Table 2
Performance of the novel CO2 cryogenic liquefaction and separation method.
Items
Mass flux of CO2 fed to the system (kg/s)
Mass flux of captured CO2 (kg/s)
CO2 recovery ratio (%)
Energy penalty for compression (MW)
Power recovered by expansion (MW)
Refrigeration capacity (MW)
Refrigeration temperature ( C)
Average COP
Energy penalty for refrigeration (MW)
Total energy penalty (MW)
Energy penalty for CO2 recovery unit (MJ/kgCO2)
is better than other two methods due to the different initial
conditions.
As is shown in Table 2, when the mass flux of liquid separated
CO2 is 89.1 kg/s, the total energy consumption of the process is
38.81 MW. The total compression work of the process is 16.90 MW,
out of which the two compressors (C1 and C2 in Fig. 5) consume
13.30 and 3.08 MW, respectively. The liquid pumps use up
0.52 MW. The consumption of the first compressor (C1) is much
greater than that of the second compressor (C2); thus, a two-stage
stage and inter-cooled compressor was adopted. For compressors
C2, the compression work is far less than that of compressor C1
because of the relatively low pressure ratio and sharp decrease in
the gas mixture. The benefits from the relatively high refrigeration
temperature (from 30 to 36  C) in this approach can be
exploited [25e27]. The average coefficient of performance of vapor
compression cycle (COP) is 1.36. The demand for refrigeration
capacity is about 27.04 MW. Then the compression work for
refrigeration is 19.85 MW. To fully recover energy, the pressure of
the purge gas (which remains at high pressure) can be expanded to
20 bar to recover 1.57 MW extra power.
3.3. Exergy analysis of the system
The exergy analysis of the system is shown in Table 3 [30]. The
transfer efficiency of the novel system, which is defined as the ratio
of the total output exergy to total input exergy, is 91.29%. The
Table 3
Exergy analysis of the novel CO2 cryogenic liquefaction and separation system.
parameter shows that the system performs well in terms of energy
utilization.
Value Table 4 shows the configuration of the exergy loss of the novel
98.87 system. The table indicates that the exergy loss of Stage 1, which
89.1 accounts for 73.28% of the total exergy loss of the entire system, is
90.0 considerably greater than that of the second stage (only 25.13%).
16.90
This result is attributed to the following: (1) The amount of gas
1.57
27.04 mixture entering Stage 1 is greater than that in the other stages. (2)
32 to 38 The compression ratio of this stage is relatively high. (3) The liquid
1.36 CO2 separated from the first stage is much greater than that from
19.85 the second stages. All of these factors cause more energy
35.81
0.395
consumption in gas mixture compression and refrigeration. Table 4
also shows that most of exergy losses lie in refrigeration and
compression, which account for 21.85% (18.73% and 3.13% for the
two stages) and 65.30% (47.63% and 17.67% for the two stages) of the
total exergy loss, respectively.
As shown in Table 4, the exergy losses of Stage 2 for compression
and refrigeration are only 3.13% and 17.67% of the total exergy loss,
a decrease by 83.29% and 62.9%, respectively, compared with those
observed in Stage 1. Except two-stage compression, two-stage
refrigeration, and two-stage separation, another effective measure
for lowering exergy loss is to make full use of the low-temperature
exergy and recover it from the entire system. The procedure is
described as follows: the lowest temperature difference of the low-
temperature heat exchangers is set as 2  C. In the low-temperature
engineering, 2  C is an acceptable choice of the pinch temperature
for low-temperature heat exchangers, such as the main heat
exchanger of Air Separation Unit (ASU) [31], which is also
a compromise result with consideration of thermodynamics and
economic performances. In detail, if the pinch temperature of the
heat exchangers decreases, which can promote the thermal
performance of heat transfer, recover more cryogenic energy, and
then reduce the capacity of external refrigeration. But the area of
the heat exchanger will increase largely, bringing much more
investment. On the contrary, a higher pinch temperature will lead
to the opposite results. In addition, the cryogenic exergy of separate
production obtains a full recovery. These measures can reduce the
demand for cryogenic exergy, thereby decreasing exergy loss in
refrigeration. In addition, the liquefaction temperature of CO2 can
be increased to a large extent by compression, consequently
improving the COP of refrigeration, which in turn reduces the
exergy loss of refrigeration.
Although the energy consumption and exergy loss of the entire
system are greatly reduced by implementing the above-mentioned

Items KW %
Exergy input Table 4
Gas mixture 184661.30 83.36% Exergy loss analysis of the novel system.
Gas compression work 16374.18 7.39%
Refrigeration work 19952.90 9.01% Items Exergy Coefficient
Liquid compression work 523.66 0.24% loss (KW) of exergy loss (%)
Subtotal 221512.05 100.00% Step 1
Exergy loss Compressor 1 3587.07 18.73%
Compressor 4186.37 1.89% Heat exchanger 1 181.76 0.95%
Heat exchanger 384.42 0.17% Separator 1 1022.57 5.34%
Separator 1620.90 0.73% Refrigeration 1 9123.76 47.63%
Refrigeration 12508.57 5.65% Pump 1 123.02 0.64%
Pump 152.34 0.07% Subtotal 14038.19 73.28%
Mixer 12.26 0.01% Step 2
Work recovered by expansion 291.27 0.13% Compressor 2 599.29 3.13%
Subtotal 19156.12 8.65% Heat exchanger 2 202.65 1.06%
Exergy output Separator 2 598.33 3.12%
Liquid CO2 62806.38 28.35% Refrigeration 2 3384.81 17.67%
Purge gas 137848.47 62.23% Pump 2 29.32 0.15%
Work recovered by expansion 1569.77 0.71% Subtotal 4814.40 25.13%
Subtotal 202224.62 91.29% Mixer 12.26 0.06%
Transfer efficiency 91.29% Power recovered by expanding 291.27 1.52%
Accuracy check (Exergy loss þ output) 99.94% Total exergy loss 19156.12 100.00%
 G. Xu et al. / Energy 42 (2012) 522e529
measures (Tables 2e4), the exergy losses of refrigeration and
compression are still the highest of the entire consumption,
accounting for nearly 87% of the total exergy loss. Therefore, the
main approach to further enhancing the performance of the system
still lies in the optimization of the refrigeration and compression
processes. Carrying out a thorough optimization of the compres-
sion processes, including the study of a high-efficiency gas
compression method, selection and optimization of different
refrigeration methods, will be effective to improve the system
performance. In addition, there are many methods in improving
refrigeration cycles. For example, (1) In consideration of the system
design of vapor compression cycle, double-stage and two-stage
compression can be adopted to increase the COP and refrigeration
capacity, then reduce the compression work. (2) In the view of the
characteristics of refrigerant, some R502 alternative refrigerants
can be considered to get a better thermodynamics performance,
such as R1270 and R290, two binary mixtures containing R1270 and
R290 and one ternary mixture containing R1270, R290 and so on
[32]. (3) From the internal units in the refrigeration system, for
example, optimization of a cooling tower assisted vapor compres-
sion refrigeration system [33]. (4) From the selection of refrigera-
tion cycles, some other cycles can be considered, such as vapor
absorption, adsorption, and steam jet refrigeration cycles. All of
these optimization measures will be the objective of future
investigations.
3.4. Investment cost estimation of the system
The novel cryogenic separation system is a fully new system. So
it is difficult to calculate its construction cost precisely. However, an
approximate estimate of the construction cost of the proposed
system can be made based on the comparison of the proposed
system with a typical air separation unit (ASU) with 2500t/
d oxygen output [34], for the sake that the two systems have many
similarities. For example, the pinch temperature in the heat
exchanger of the proposed system is 2  C, which is similar with the
main heat exchanger of air separation unit (ASU). And the heat
transfer capacity of low-temperature heat exchangers and the
energy consumption of compressors are approximately equal in
two systems. Besides, the lowest temperature of ASU can
reach 160  C or so, which is much lower than the proposed
system, as well as a costly distillation unit with two towers.
Therefore, to estimate approximately, the investment cost of the
proposed system will be not higher than that of ASU with 2500 ton/
day oxygen output. And the cost of a typical ASU with 2500 ton/day
oxygen output is about 47.1Million US dollars (M$) [34].
That is, the investment cost of the proposed system should be
less than 47.1M$ (with CO2 captured capacity of 89.1 kgCO2/s). In
comparison, the construction costs of a typical MEA absorption
process and a typical Selexol absorption process are about
160e170M$ (87.3 kgCO2/s) and 65e110M$ (160 kg/s), respectively
[28,29]. In conclusion, in a rough estimation, the construction cost
of proposed system is lower than that of typical MEA absorption
process and close to that of typical Selexol absorption process.
4. Discussion
4.1. Influence of initial pressure and concentration on CO2 capture
energy consumption
The initial pressure and concentration of the mixture have
significant effects on the system performance. Fig. 6 shows the
relationship between the energy penalty for CO2 capture (per
kgCO2) and the initial pressure and CO2 concentration of the gas
mixture. The energy penalty for CO2 capture sharply increases as
527
1.6
CO2 capture energy penalty (MJ/kgCO2)
1.4
1.2
1.0
0.8
0.6
0.4
0.2
40 50 60 70 80 90
CO2 initial mole concentration (%)
Fig. 6. Relationship of CO2 capture energy penalty and initial CO2 mole concentration
at different initial mixture pressures.
the initial CO2 concentration decreases. Compared with the energy
penalty at an initial concentration of 80%, that at 60% concentration
increases by 50%e60%. In addition, it increases by 140%e160% at an
initial concentration of 40%. These results are attributed to the
following factors: (1) the lower the initial CO2 concentration, the
lower the CO2 condensation temperature (Figs. 2e4), leading to
more energy consumption in the refrigeration of the gas mixture;
and (2) with the decrease in initial CO2 concentration, the pressure
of the gas mixture should be increased further to raise the CO2
condensation temperature to a higher level (Figs. 3 and 4), causing
more substantial compression work.
Fig. 6 also shows that the energy penalty for CO2 capture can
dramatically decrease with increasing initial pressure. In the
proposed system, compressing the gas mixture to an appropriate
pressure of as high as 30e80 bar is necessary to maintain CO2
condensation temperature at a relatively high level (above 45  C).
The higher the initial pressure, the less substantial the compression
work, leading to the decrease in the energy penalty for CO2 capture.
In conclusion, the proposed CO2 cryogenic liquefaction and
separation system is more suitable for separating liquid CO2 from
gas mixtures with high CO2 concentration. Moreover, a higher
initial pressure of the mixture presents better performance.
4.2. Influence of initial CO2 concentration on final mixture pressure
and CO2 purity
Fig. 7 shows the influence of initial CO2 concentration on the
purity of CO2 liquid and final pressure of the mixture when the CO2
recovery ratio remains at 90%. When the initial concentration of the
gas mixture ranges from 30% to 90%, the purity of the liquid CO2
separated from the novel system can reach more than 99%, which
satisfies the universal requirement for CO2 transportation and
storage. This result indicates that the novel CO2 cryogenic lique-
faction and separation system can reach a satisfactory purity level
for CO2 products at a relatively wide range of initial CO2
concentration.
Meanwhile, the final pressure of the mixture decreases as initial
CO2 concentration increases. At an initial CO2 concentration of 30%,
the final pressure of the gas mixture is as high as 78 bar. By contrast,
at an initial concentration of 90%, the final pressure is only 36 bar.
Such varying trends conform to those depicted in Figs. 3 and 4; that
is, at a sufficiently high CO2 concentration of the mixture,
528
90
80
Liquid Production
Pressure (bar)
70
60 Final-stage Mixture
50
40
30
20 30 40 50 60 70 80
CO2 Initial Mole Concentration (%)
Fig. 7. Influence of initial CO2 mole concentration on final mixture pressure and
production concentration.
a relatively low pressure of the gas mixture can guarantee high
levels of CO2 partial pressure and liquefaction temperature.
To conclude, in the proposed CO2 cryogenic liquefaction and
separation system, the final pressure of gas mixture decreases
along with the increase in initial CO2 concentration. The novel
method can achieve CO2 capture with high recovery ratio and
product purity within a relatively wide range of initial CO2
concentrations. Especially, it is more suitable for the gas mixture
with high initial CO2 concentration.
5. Conclusion
On the basis of the in-depth analysis of the characteristics of the
cryogenic separation method, this paper proposes a novel CO2
cryogenic liquefaction and separation system. The following
conclusions are drawn from the theoretical analysis and case study:
(1) An appropriate compression of gas mixture can improve the
performance of cryogenic separation.
Fig. 3 and Section 2 show that an appropriate mixture
compression can enhance liquefaction temperature, thereby
decreasing the energy penalty for refrigeration and reducing the
total energy penalty for CO2 capture. This conclusion was also well
verified by the analysis of the proposed CO2 cryogenic liquefaction
and separation system (Section 3).
(2) Two-stage compression, two-stage refrigeration, two-stage
separation, and sufficient recovery of cryogenic energy can
improve performance.
All these measures contribute to the decrease in the total energy
consumption for CO2 capture due to less cryogenic energy demand
and compression work, as well illustrated in the analysis of the
proposed system (Section 3).
(3) The proposed system can achieve good comprehensive
performance.
Under a recovery ratio of 90%, the proposed CO2 cryogenic
liquefaction and separation system can produce high-purity CO2
product (above 99%) within a relatively wide range of initial CO2
concentrations (as shown in Fig. 7). In addition, the energy
consumption for CO2 recovery in the proposed system is only
0.395 MJ/kgCO2.
G. Xu et al. / Energy 42 (2012) 522e529
(4) The higher the initial mixture pressure and initial CO2
100 concentration, the lower the energy consumption of the
99
proposed system.
CO2 Concentraion (%)
98 Fig. 6 shows that the proposed CO2 cryogenic liquefaction and
separation system is more suitable for separating liquid CO2 from
97
gas mixtures with high CO2 concentration. In addition, higher
96 initial pressure of the mixture presents better performance.
95
Acknowledgments
94
93 The paper is supported by National Nature Science Fund of
China (No. 51006034, No. 51025624), and the National Major
92
90 100
Fundamental Research Program of China (No. 2009CB219801, No.
2011CB710706).
References
[1] Working group III of the intergovernmental panel on climate change. IPCC
special report on carbon dioxide capture and storage. Cambridge, United
Kingdom: Cambridge University Press. Available from: http://www.ipcc-wg3.
de/publications/special-reports/special-report-on-carbon-dioxide-capture-
and-storage; 2005.
[2] Working group I of the intergovernmental panel on climate change. IPCC’s fourth
assessment report (AR4): climate change 2007 the physical science basis.
Cambridge, United Kingdom: Cambridge University Press. Available from:
https://www.ipcc-wg1.unibe.ch/publications/wg1-ar4/wg1-ar4.html; 2007.
[3] Riemer P. Greenhouse gas mitigation technologies, an overview of the CO2
capture, storage and future activities of the IEA greenhouse gas R&D program.
Energy Conversion and Management 1996;37:665e70.
[4] Lior N. Energy resources and use: the present (2008) situation and possible
sustainable paths to the future. Energy 2010;35:2631e8.
[5] Zhang N, Lior N, Jin H. The energy situation and its sustainable development
strategy in China. Energy 2011;36:3639e49.
[6] Xu G, Jin H, Yang Y, Duan L, Han W, Gao L. A novel coal-based hydrogen
production system with low CO2 emissions. ASME Journal of Engineering for
Gas Turbines and Power 2010;132:031701-9.
[7] Hammonda GP, Ondo Akwea SS, Williams S. Techno-economic appraisal of
fossil-fuelled power generation systems with carbon dioxide capture and
storage. Energy 2011;36:975e84.
[8] Ramezan M. Carbon dioxide capture from existing coal-fired power plants. Final
report. National Energy Technology Laboratory. Available from: http://www.
netl.doe.gov/energy-analyses/pubs/CO2%20Retrofit%20From%20Existing%
20Plants%20Revised%20November%202007.pdf; 2007 Nov.
[9] Edward S, Anand B. A technical, economic, and environmental assessment of
amine based CO2 capture technology for power plant greenhouse gas control,
annual technical progress report. Carnegie Mellon University Center for
Energy and Environmental Studies [Contract No.: DE-FC26e00NT40935].
Available from: http://repository.cmu.edu/epp/94/; 2002 Oct.
[10] Rezvani S, Huang Y, McIlveen-Wright D, Hewitt N, Mondol J. Comparative
assessment of coal fired IGCC systems with CO2 capture using physical
absorption, membrane reactors and chemical looping. Fuel 2009;88:2463e72.
[11] Jockenhoevel T, Schneider R, Rode H. Development of an economic post-
combustion carbon capture process. Energy Procedia 2008;00:1043e50.
[12] Yan S, Fang M, Zhang W, Zhong W, Luo Z, Cen K. Comparative analysis of CO2
separation from flue gas by membrane gas absorption technology and
chemical absorption technology in China. Energy Conversion and Manage-
ment 2008;49:3188e97.
[13] Sayari A, Belmabkhout Y, Serna-Guerrero R. Flue gas treatment via CO2
adsorption. Chemical Engineering Journal; 2011.
[14] Sjostrom S, Krutka H. Evaluation of solid sorbents as a retrofit technology for
CO2 capture. Fuel 2010;89:1298e306.
[15] Mavroudi M, Kaldis S, Sakellaropoulos G. Reduction of CO2 emissions by
a membrane contacting process. Fuel 2003;82:2153e9.
[16] Zhao L, Riensche E, Menzer R, Blum L, Stolten D. A parametric study of CO2/N2
gas separation membrane processes for post-combustion capture. Journal of
Membrane Science 2008;325:284e94.
[17] Zhang N, Lior N. A novel near-zero CO2 emission thermal cycle with LNG
cryogenic exergy utilization. Energy 2006;31:1666e79.
[18] Zhang N, Lior N. Two novel oxy-fuel power cycles integrated with natural gas
reforming and CO2 capture. Energy 2008;33:340e51.
[19] Zhang N, Lior N, Liu M, Han W. COOLCEP (cool clean efficient power): a novel
CO2-capturing oxy-fuel power system with LNG (liquefied natural gas) cold-
ness energy utilization. Energy 2010;35:1200e10.
[20] Zanganeh KE, Shafeen A, Salvador C. CO2 capture and development of an
advanced pilot-scale cryogenic separation and compression unit. Energy
Procedia 2008;1:247e52.
 G. Xu et al. / Energy 42 (2012) 522e529
[21] Amann JM, Kanniche M, Bouallou C. Natural gas combined cycle power plant
modified into an O2/CO2 cycle for CO2 capture. Energy Conversion and
Management 2009;50:510e21.
[22] Tuinier MJ, Annaland MS, Kramer GJ, Kuipers JAM. Cryogenic CO2 capture
using dynamically operated packed beds. Chemical Engineering Science 2010;
65:114e9.
[23] Hart A, Gnanendran N. Cryogenic CO2 capture in natural gas. Energy Procedia
2009;1:697e706.
[24] Tsang CY, Streett WB. Phase equilibria in the H2/CO2 system at temperatures
from 220 to290 K and pressures to 172 MPa. Chemical Engineering Science
1981;36:993e1000.
[25] Arora A, Kaushik SC. Theoretical analysis of a vapour compression refrigera-
tion system with R502, R404A and R507A. International Journal of Refriger-
ation 2008;31:998e1005.
[26] Wang SH. Handbook of air conditioning and refrigeration. 2nd ed. New York:
McGraw-Hill; 2001.
[27] Dalkilic AS, Wongwises S. A performance comparison of vapour-compression
refrigeration system using various alternative refrigerants. International
Communications in Heat and Mass Transfer 2010;37:1340e9.
529
[28] Parsons EL, Shelton WW, Lyons JL. Advanced fossil power systems
comparison study. Available from: www.netl.doe.gov/publications/others/
techrpts/AdvFossilPowerSysCompStudy.pdf; 2002.
[29] IEA GHG. Potential for improvements in gasification combined cycle power
generation with CO2 capture. Report No. PH4/19. Available from: http://www.
ieaghg.org/index.php?/ieaghg-technical-reports.html; 2003.
[30] Gao L, Jin H, Liu Z, Zheng D. Exergy analysis of coal-based polygeneration
system for power and chemical production. Energy 2004;29:2359e71.
[31] Li HZ. Oxygen production technologies. 2nd ed. Beijing: Metallurgical Industry
Press; 2009 [in Chinese].
[32] Park KJ, Jung D. Thermodynamic performance of R502 alternative refrigerant
mixtures for low temperature and transport applications. Energy Conversion
and Management 2007;48:3084e9.
[33] Sayyaadi H, Nejatolahi M. Multi-objective optimization of a cooling tower
assisted vapor compression refrigeration system. International Journal of
Refrigeration 2011;34:243e56.
[34] Kreutz T, Williams R, Consonni S, Chiesa P. Co-production of hydrogen, elec-
tricity, and CO2 from coal with commercially ready technology. Part B:
economic analysis. International Journal of Hydrogen Energy 2005;30:769e84.