Applied Energy 200 (2017) 119–131

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Performance evaluation of CO2 capture with diethyl succinate

Hongwei Li a, Zhigang Tang b,⇑, Zhimin He b, Jingjie Cui b, Dong Guo b, Zhijun Zhao b, Xian-zhong Mao a,⇑
a
Division of Ocean Science and Technology, Graduate School at Shenzhen, Tsinghua University, Shenzhen, PR China
b
State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing, PR China

h i g h l i g h t s

Diethyl succinate (DES) is a new and highly efficient CO2 absorption solvent.

Solubility of CO2 in the DES was obtained by experiment and predictive models.

Continuous CO2-DES absorption-desorption experiments were carried out.

A novel desorption process of CO2-DES was applied to simplify the continuous process.

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

Article history: Diethyl succinate (DES) is a new and highly efficient carbon dioxide (CO2) absorption solvent. Vapor-
Received 6 December 2016 liquid equilibrium data for the CO2 + DES system were obtained experimentally from 288.15 K to
Received in revised form 12 April 2017 318.15 K by the gas-phase recirculation method, and were modeled using the Kritchevsky-Kasarnovsky
Accepted 3 May 2017
model and Peng-Robinson equation of state. The vapor-liquid equilibrium data of the DES system were
Available online xxxx
compared with those of the diethyl carbonate (DEC) and dimethyl carbonate (DMC) systems, and
Henry constant was found to follow DES < DEC < DMC. The absorbed and released energy as simulated
Keywords:
using Gaussian 09 software shows that the CO2 absorption capacity of DES is better than that of the
CO2 capture
Diethyl succinate
DEC and DMC. A continuous absorption-desorption experimental setup was established for the CO2-
Solubility measurement DES system to determine the optimum operating conditions of a liquid-gas ratio of 1.337, an absorption
Predictive model temperature range from 291.15 to 293.15 K, a desorption temperature range from 433.15 to 443.15 K,
Molecular simulation and a nitrogen (N2) flow of 0.5 NL/min. The DES system costs less than the DEC and DMC systems when
Continuous absorption-desorption process using N2 gas-stripping desorption. A novel desorption process with compression and condensation was
used to regenerate solvent and to simplify the process. This system costs less than those for thermal des-
orption, and gas-stripping desorption. The results from the DES system were better than those of the DMC
and DEC systems. DES shows potential as a CO2 absorbent.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
With ever-increasing fossil-energy consumption, carbon emis-
sions have exceeded ecological environmental tolerances, which
has resulted in an increase in global temperature, polar glacier
melting, and frequent extreme changes in weather and climate
[1,2]. At the 2015 Paris Climate Change Conference, 195 nations
committed to ‘‘holding the increase in the global average temper-
ature to well below 2 °C above pre-industrial levels and to pursue
efforts to limit the temperature increase to 1.5 °C above
pre-industrial levels, recognizing that this would significantly
reduce the risks and impacts of climate change”. The historic Paris
⇑ Corresponding authors.
E-mail addresses: zhg-tang@tsinghua.edu.cn (Z. Tang), maoxz@sz.tsinghua.edu.
cn (X.-z. Mao).
Agreement was forged under the United Nations Framework Con-
vention on Climate Change, and ended a long-lasting political
deadlock [3–7]. As a major greenhouse gas-emitting nation and a
responsible world power, the Chinese government committed to
cut its carbon dioxide (CO2) emissions per unit of gross domestic
product by 60–65% by 2030 relative to its 2005 levels and peak
CO2 emissions around 2030 and make best efforts to peak earlier
on June 30, 2015 [8]. At the Hangzhou G20 summit on September
4–5, 2016, China announced its intention to ratify the Paris Agree-
ment, and encouraged all G20 members to follow suit. China also
created the ‘‘Green Finance Study Group”, which was tasked with
identifying institutional and market barriers to green finance and
options to enhance the mobilization of private funds for green
investment [9]. CO2 emission reduction is required urgently. CO2
capture and storage is regarded as a great potential way to reduce
CO2 emissions [10–12]. However, its high capture cost restricts its

http://dx.doi.org/10.1016/j.apenergy.2017.05.036
0306-2619/Ó 2017 Elsevier Ltd. All rights reserved.
120 H. Li et al. / Applied Energy 200 (2017) 119–131
development. Therefore, greenhouse-emission-reduction research
has focused on searches for novel and efficient CO2 absorbents,
reductions in desorption-energy consumption, and improvements
of absorption equipment. The integrated gasification combined
cycle (IGCC) [13,14] has a high power-generation efficiency and
is regarded as a potential and clean-coal power-generation tech-
nology. A combination of IGCC with capture and storage is
expected to achieve near-zero CO2 emissions. Pre-combustion
CO2 capture is applied to IGCC system for its high synthesis gas
pressure [15–17].
Physical absorbents are better than chemical solvents at a high
gas pressure, as shown by comparing several mature CO2 absor-
bents [18,19]. Industrial processes for CO2 capture with physical
solvents include mainly the Rectisol process (with methanol absor-
bent) [20,21], the Flour process (propylene carbonate, PC) [22], the
Selexol process (polyethylene glycol dimethyl ether) [23,24], and
the Purisol process (N-methyl pyrrolidone) [25], which have a
highly efficient CO2 absorption capacity. However, methanol has
a high cooling power consumption and high toxicity. Polyethylene
glycol dimethyl ether, PC, and N-methyl pyrrolidone require a large
amount of energy during solvent regeneration and are expensive.
Therefore, it is essential to search for novel and efficient CO2
absorbents.
Some studies on the development of novel physical CO2 absor-
bents have shown that dimethyl carbonate (DMC) is considered to
be an environmentally-acceptable, high-performance absorbent
[26–30]. The solubility of CO2 in DMC is 50% higher than that of
CO2 in PC at the same temperature and CO2 absorption effect by
DMC at room temperature is better than that of methanol at low
temperature. The viscosity of DMC increases rapidly with decreas-
ing the temperature, even DMC can solidify at a low temperature
because of its high DMC freezing point of 275.15 K. DMC’s solvent
loss is high because of its low boiling point of 363.22 K. Diethyl car-
bonate (DEC) [31,32] performs better than DMC in terms of CO2
absorption. However, DEC’s solvent loss is also high because of
its low boiling point of 398.95 K. This paper presents a new high-
efficiency CO2 solvent, diethyl succinate (DES), which has a low
volatility and nearly zero solvent loss and studies on the CO2
absorption capacity of the DES.
Extensive research exists on phase-equilibrium data for the bin-
ary CO2-DES system. Feng et al. [33] obtained CO2-DES vapor-
liquid-equilibrium (VLE) data by a semi-flow type apparatus at
308.15, 318.15 and 328.15 K from 1.0 to 13 MPa. Li [34] used the
constant-volume method to measure the solubility of CO2 in DES
at 298.15 K and 0.099–0.504 MPa. Gui et al. [35,36] also used the
constant-volume method to measure the solubility of CO2 in DES
at 285.19–313.26 K and 0.0636–1.7878 MPa. These methods
obtain VLE data by indirect measurement and calculation.
A number of studies have focused on the prediction of CO2-
solvent phase equilibrium. Ai [37] and Gui [35] used the
Prausnitz-Shair method, which was based on the activity-
coefficient method. It can be used to calculate the solubility at a
CO2 partial pressure of 100 kPa, and requires many parameters.
Li [34] used the molecular-connectivity index method, which
was based on solvent molecular structure to characterize inter-
molecular forces. This method can be used to calculate the solubil-
ity characteristic (lg H) of CO2 in solvent, but has a large relative
error. Many authors have used the equation-of-state method, espe-
cially the Peng-Robinson equation, which has a high accuracy [33].
Extensive research exists to simulate CO2 capture process. Liu
[38] and Li [39] used a detailed arrangement of four columns to
simulate the CO2 capture process, which included an absorber, a
desorber, a water wash tower, and a stripping tower. Gui [35] sim-
plified the simulation by removing the water wash and stripping
towers, and used thermal desorption to regenerate solvent. Li
[34] simplified the process further by using flash, compression,
and condensation stages to regenerate solvent. We produced a
set of process apparatus to evaluate the performance of CO2 cap-
ture by DES.
The above methods, which include the semi-flow-type method
and the constant-volume method, provide VLE data by indirect
measurement and calculation, whereas in this work, the gas-
phase recirculation method with direct measurement of gas com-
position was used to measure the phase equilibrium data of the
CO2-DES system. The VLE data were modeled by using the
Kritchevsky-Kasarnovsky (K-K) [44] method and the Peng-
Robinson equation of state (PR EOS) [45,46], and were analyzed
by molecular simulation using Gaussian 09 software. A continuous
absorption-desorption experimental apparatus was designed to
evaluate the ability of the DES to capture CO2 in the process. The
different CO2-DES processes were simulated by using Aspen Plus
2006 to identify the cheapest and simplest option. DES was com-
pared with DEC and DMC to assess its CO2 capture properties.
2. Experimental section
2.1. Materials
CO2 with a volume fraction of 0.9999 was supplied by Beiwen
Gas, Beijing, China. DES (C8H14O4, with a mass fraction of 0.999)
was from Aladdin Reagent Company, Shanghai, China. Properties
of the DES, DEC, and DMC are shown in Table 1.
2.2. CO2-DES VLE experimental apparatus
The VLE data between CO2 and DES were determined by the
gas-phase recirculation method. A schematic diagram of the exper-
imental apparatus is shown in Fig. 1. The apparatus includes an
equilibrium cell, a gas-phase recirculation line, and a gas chro-
matograph (GC). The equilibrium cell made of type-316 stainless
steel had an inner volume of approximately 1000 mL and an alarm
pressure of 10.0 MPa. A stirrer, which was rotated at variable
speeds by an external magnet, accelerated the attainment of equi-
librium. The temperature was monitored using a Pt-100 resistance
thermometer with an uncertainty of ±0.1 K. Pressure was mea-
sured using a 0.5% diffusion silicon pressure transducer with an
uncertainty of ±0.02 MPa. The gas in the equilibrium cell was with-
drawn from the top of the equilibrium cell by a metering pump
through the gas sample valve, and it was sent into the equilibrium
cell from the bottom, which achieved gas-phase recirculation and
accelerated the gas-liquid equilibrium. The circulation line and
gas sample valve temperature were maintained by using foam
insulation. Online analysis of the equilibrium composition was car-
ried out using a GC (GC 7800, Purui Company, Beijing, China) with
an uncertainty of ±0.03. The GC was equipped with a thermal con-
ductivity detector (TCD) and a 2-m-long, and 3-mm-diameter
Porapak Q column. The carrier gas was hydrogen, with a flow rate
of 30 mL/min. The injection, TCD, and GC column temperatures
were 493.15, 473.15, and 453.15 K, respectively. The TCD current
was 100 mA.
Experiments to obtain the VLE data for the binary CO2-DES sys-
tem were as follows. Approximately 500 mL of DES was injected
into the equilibrium cell. The cell temperature was maintained
by controlling the temperature of the water bath and a certain
amount of N2 was injected into the equilibrium cell, whose tem-
perature and pressure were recorded. A certain amount of CO2
was injected into the equilibrium cell, whose temperature and
pressure were also recorded. The magnetic stirrer was started to
accelerate gas-liquid equilibrium attainment. After the tempera-
ture and pressure in the equilibrium cell had remained constant
for more than 30 min, equilibration was achieved, and the final
pressure and temperature were recorded. A gas sample was with-
 H. Li et al. / Applied Energy 200 (2017) 119–131 121

Table 1
Properties of solvents for CO2 capture.

Material Molecular weight (g/mol) Melting point (K) Boiling point (K) Density (gcm3) TC (K) PC (MPa) x
CO2 44.01 216.55 194.65 1.56 304.2 7.38 0.225
DES 172.20 252.15 490.85 1.05 660.0 2.53 0.737
DEC 118.13 230.15 398.95 0.98 576.0 3.39 0.485
DMC 90.08 273.15 363.22 1.07 548.0 4.50 0.385

TC: critical temperature and PC: critical pressure.

V3
V4
6
PC P 2
TC T
V1
1
4 5
8

3
G1 G2 V2

Fig. 1. Schematic of gas-phase recirculation apparatus: (1) equilibrium cell, (2) gas chromatograph, (3) computer, (4) primary filter, (5) precision filter, (6) gas sample valve,
(7) water bath, (8) metering pump, G1: N2 gas cylinder, G2: CO2 gas cylinder, V1–V4: valves, TC: temperature measurement, PC: pressure measurement.

drawn from the equilibrium cell by using a recycling pump and
sample was injected immediately into the GC, via a gas sample
valve, for analysis. Because the withdrawn sample volume is very
small (1 lL) compared with the total volume inside the equilib-
rium cell (500 mL), it is possible to withdraw many samples
without disturbing the studied phase equilibrium significantly. At
least five analyses were performed for each phase with an average
value considered to correspond with the equilibrium value.
The data processing was as follows: first, it was necessary to
formulate a standard curve by using a CO2/N2 standard gas of
4.81%, 15.7%, 25.1%, 50.7%, and 74.8% CO2 volume fraction using
GC, as shown in Fig. 2. Second, the CO2 content in the equilibrium
3.5
3.0
2.5
2.0
ACO2/AN2
cell was obtained by analyzing the gas-phase samples by GC.
Finally, the solubility of CO2 in the solvent was determined from
the CO2 concentration difference between the initial and equilib-
rium samples.
2.3. CO2-DES continuous absorption-desorption system
To evaluate the ability of the DES to capture CO2, a continuous
absorption-desorption experimental apparatus was designed, the
schematic diagram of which is shown in Fig. 3. The apparatus
includes an absorber, flash tanks, a desorber, a product scrubber,
and a desorption gas scrubber. The experimental apparatus was
equipped with a real-time control system, which was integrated
with the measurement data into a user interface. The details of
the experimental apparatus and experimental procedure have
been described previously [27,32,40].
Parameters for the simulated gas were a 15 NL/min flow at
298.15 K and 3.10 MPa, and with a CO2 mole fraction of 38.81%
and the remainder air [41]. The absorber pressure was 3.10 MPa,

whereas the desorber was set to atmospheric pressure.

The next step was data processing. Three parameters were used
1.5
to evaluate the CO2-DES continuous absorption-desorption
y=1.05383x+0.01516 process
1.0
R2=1
(1) CO2 absorptivity, or recovery rate, was defined as the ratio
0.5 between the molar quantity of captured CO2 and the molar
quantity of CO2 in the feed as described by Eq. (1) with an
0.0 uncertainty of 0.020:
0.0 0.5 1.0 1.5 2.0 2.5 3.0
xCO2/xN2 molar quantity of captured CO2 C in  C out
gCO2 ¼ ¼ ð1Þ
the total molar quantity of CO2 C in ð1  C out Þ
Fig. 2. Standard curve of CO2/N2 standard gas (x:xCO2; y:ACO2/AN2).
122 H. Li et al. / Applied Energy 200 (2017) 119–131

into infra-red analyzer into infra-red analyzer

into infra-red analyzer T3

F1 F2 into the air

T1 T2
V1
T4
water
out

CO1 CO2 CO3 V2

V3
G1 G2
water
in
C1 P1 P2
Fig. 3. Schematic diagram of CO2-DES continuous absorption-desorption system: T1: absorber, T2: desorber, T3: product scrubber, T4: desorption gas scrubber, CO1–3: heat
exchangers, F1–2: flash tanks, P1: absorbent pump, P2: water pump, V1: gas mixing tank, V2: absorbent storage tank, V3: water tank, G1: CO2 gas cylinder, G2: N2 gas
cylinder, C1: cooler.

where Cin and Cout represent the mole fraction of CO2 in the absorber
inlet and outlet, respectively.
(2) The liquid-gas ratio (L/V) expresses the molar ratio between
DES and the feed gas. It has a direct influence on the absorp-
tion effect and is expressed by Eq. (2) with an uncertainty of
0.050:
22:4  qL F L
L=V ¼
60  F G  M L
where FG is the gas volume through the absorber per unit
time (NL/min), FL is the absorbent volume through the absor-
ber per unit time (NL/h), ML is molar mass of the liquid (kg/-
mol), and qL is the density of the absorbent (kg/NL).
(3) Energy consumption, which is assumed to be a combination
of the following factors:
(a) Pumping power, as described by Eq. (3) with an uncertainty
of 0.010 J/s [42]:
where mCO2 is the total mass of captured CO2 in the process.
Flow, composition, temperature, pressure, and operating-
parameter data of the absorber and desorber were obtained in
the experimental process, and the heating and cooling duty were
simulated using Aspen Plus.
To compare the operating costs for thermal desorption and gas-
stripping desorption, the system energy consumption, solvent loss,
ð2Þ and capture cost were calculated. Items’ costs in the CO2-DES
absorption-desorption system are shown in Table 2. The cost of
cooling was evaluated by calculating the amount of cooling water
(specific heat capacity 4182 J/kgK with a permissible temperature
change of 7 K) and multiplying the cost with the price of cooling
water. The heating energy consumption was evaluated by multi-
plying the amount of required water vapor (latent heat of vapor-
ization was 2243.9 kJ/kg) by its price.
2.4. Predictive models for CO2-DES VLE

ðP2  P 1 Þ  106 þ qL gðH2  H1 Þ Reliable solubility data for CO2 in DES is scarce, especially far
W LP ¼ F L  ð3Þ
1000  3600  gLP from 298.15 K. Owing to the complexity of the gas-liquid system,
different researchers have reported varying data for similar system
where FL is the volumetric flow of absorbent through the conditions. Therefore, further study is required to develop predic-
absorber per unit time (NL/h); P1 and P2 are the pressure tion models for gas solubility.
before and after the pump, respectively (MPa); qL is the den-
sity of the absorbent (kg/m3); H1 and H2 are the height before
2.4.1. K-K model
and after the absorbent was conveyed (m); gLP is the effi-
The K-K model is a modified Henry’s law, which can be used to
ciency of the absorbent pump, which is assumed to be 0.78;
calculate the solubility of undissolved gas in solvent at high pres-
and g is the gravitational acceleration, 9.8 N/kg.
sure and broaden its scope of application. Henry’s law applies to
(b) The thermal load of the desorber (QRB) as calculated from the
a special system where the solute gas pressure is an atmospheric
simulation of thermal desorption.
pressure and when the solute undergoes no chemical reaction or
(c) The energy consumption for cooling (QC) as calculated from
solvent association. Henry’s law assumes ideal-gas behavior, so it
the simulation.
(d) The energy consumption of the heat exchanger, where
energy is transferred between the barren and the rich Table 2
liquors, was an internal heat exchange within the system, CO2-DES absorption–desorption system costs.
and can be ignored. The energy consumption of the heat Items Prices [43]
exchanger to maintain the feed temperature for the absorber
Electricity 0.6 Yuan RMB/kW  h
(QH), was calculated from the simulation. DES 25,000 Yuan RMB/ton
(e) The total energy consumption per unit mass of captured CO2, Cooling water 0.8 Yuan RMB/ton
as described by Eq. (4) with an uncertainty of 0.001 J/kgCO2: Water vapor 120 Yuan RMB/ton
N2 0.5 Yuan RMB/Nm3
ET ¼ ðW LP þ Q RB þ Q C þ Q H Þ=mCO2 ð4Þ 1 Yuan RMB = 0.1476 USD, as at November 2016.
 H. Li et al. / Applied Energy 200 (2017) 119–131 123

is not applicable when the gas pressure increases. Henry constant Table 3
(H) at atmospheric pressure is a function of temperature and sol- Parameter settings of models in CO2-DES absorption-desorption system.

vent type, whereas H at a high pressure is a function of tempera- Model Model Parameter settings Function
ture, solvent type, and pressure. H changes with pressure when type
the solvent types and temperature are given. The K-K model con- T1 RADFRAC 8 stages, no condenser, no reboiller, Absorb
siders the influence of pressure on solubility and broadens the 3.1  103 kPa of top-stage pressure,
scope of application of Henry’s law. The K-K Model is shown in 20 kPa of column pressure drop

Eq. (5) [44]: T2 RADFRAC 7 stages, no condenser, kettle reboiller, Desorb

101.325 kPa of top-stage pressure,
f2 pCO2 V 2 103.325 kPa of 7th stage pressure
ln ¼ ln K 0 þ ð5Þ T3 RADFRAC 7 stages, no condenser, no reboiller, Product
x2 RT
110 kPa of top-stage pressure, 2 kPa of scrub
column pressure drop
where subscripts 1 and 2 denote DES and CO2, respectively; V 2 is
the partial molar volume of the gas in the liquid phase; K’ is the T4 RADFRAC 7 stages, no condenser, no reboiller, Desorption
110 kPa of top-stage pressure, 2 kPa of gas scrub
modified Henry constant; pCO2 is the partial pressure of CO2; x is
column pressure drop
the solubility of CO2 in a solvent, and f is the fugacity of the gas
F1 FLASH2 600 kPa of flash pressure, zero heat duty Gas–liquid
solute.
separation
F2 FLASH2 400 kPa of flash pressure, zero heat duty Gas–liquid
2.4.2. PR equation of state separation
It is important to investigate the equation of state and the
parameters that describe the relationship between the gas-liquid
composition and the system temperature and pressure. Model 2.6. Process simulation
parameters are usually derived by fitting experimental data from
the binary system. In this work, the PR equation of state with the The CO2-DES continuous absorption-desorption experiment has
Van der Waals mixing rule was used for the CO2-DES system. The a long operating period, and some limitation on practical operating
PR equation is [45,46]: conditions. To study the impact of various operating conditions on
RT aa the system, this process was simulated in Aspen Plus 2006 using
p¼  ð6Þ the same parameters as in the experimental set up and using the
V  b V 2 þ 2bV  b2
PR EOS method. Model details are shown in Table 3. By combining
experiments with simulations, it was possible to investigate the
a ¼ 0:45725R2 T 2c =Pc ð7Þ optimal operating conditions.

b ¼ 0:0778RT c =Pc ð8Þ

3. Results and discussion
h
i2
a ¼ 1 þ ð0:37464 þ 1:54226x  0:26992x2 Þ 1  T 0:5
r ð9Þ 3.1. CO2-DES phase equilibrium

PP P qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
where aa ¼ aÞij , b ¼ ðaaÞij ¼ ð1  kij Þ ðaaÞi ðaaÞj , The validity of the experimental system was determined first by
i j yi yj ða i yi bi ,
measuring the VLE data for a binary mixture of CO2 and PC at
kij ¼ kji , kii ¼ 0, kij is the binary interaction parameters, Tc is the crit- 298.15 K and 313.15 K. The experimental results are shown in
ical temperature, pc is the critical pressure, and x is the acentric Fig. 4. The measured results using the gas-phase recirculation
factor. apparatus agree well with those in the previous literature
TC, PC, and x for CO2 and DES that are used to calculate param- [37,49,50] with less than 5% relative error.
eters for the PR-EOS are provided in Table 1. The PR-EOS parame- Phase-equilibrium data for the CO2-DES binary system at
ters are obtained by minimizing the following objective function. 288.15, 298.15, 308.15, 313.15, and 318.15 K were measured.
" ! #2
1X n
pk;exp  pk;cal
Objectiv e function ¼  100 ð10Þ
n k¼1 pk;exp 2.5
313.15K 298.15K
[50] [50]
where the subscripts exp and cal represent the experimental and 313.15K 298.15K
2.0 [49] [49]
calculated values, respectively. 313.15K 298.15K
[37]
313.15K
2.5. Molecular simulation 1.5
p/MPa

Because of difficulties in the experimental research, it is impor-

1.0
tant to understand the intrinsic features by molecular interaction.
Gaussian theory [47,48] can reflect the essence of physical and
chemical phenomena at a molecular level and predict the relation- 0.5
ship between molecular structure and property, for example, inter-
atomic cohesive energy, which guides the molecular design of an
efficient absorbent. Gaussian theory can simulate the molecular 0.0
0.00 0.05 0.10 0.15 0.20 0.25
interaction energy based on an appropriate calculation method.
xCO2
Gaussian 09 software is applicable to simulate the interaction
energy of the solvent molecules and that between the solvent Fig. 4. Experimental solubility of CO2 in PC compared with literature data (solid
molecule and CO2. The software was used to study the perfor- points denote experimental data, and hollow points and lines denote literature
mance of a solvent to capture CO2 at a molecular level. data).
124 H. Li et al. / Applied Energy 200 (2017) 119–131

4 [35]
4
298.15K 298.15K 288.15K 298.15K
[33] 308.15K 313.15K
308.15K 308.15K
[33]
3 318.15K
318.15K 318.15K
3 K-K Model

p/MPa
288.15K
313.15K 2
p/MPa

2 1

1.0
0

1
0.5

x/x(%)
0.0
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
x CO2 -0.5

Fig. 5. Solubility of CO2 in DES (solid points denote experimental data and hollow
points denote literature data). -1.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
xCO2
These results were compared with data reported by others, which
Fig. 6. Comparison of calculated and experimental data from the K–K model and
were derived using other methods, as shown in Fig. 5. Fig. 5 shows
relative deviations.
that the results from the various methods (constant volume [35],
semi-flow type method [33], and gas-phase recirculation method)
show slight deviations but are largely consistent with less than 5%
Table 5
relative error. The gas-phase recirculation method results agree Binary interaction parameters kij for PR EOS and relative deviations.
well with those from the constant-volume method, but data mea-
T (K) 288.15 298.15 308.15 313.15 318.15
sured by constant volume are obtained by indirect calculation,
kij 0.0253 0.0132 0.0157 0.0151 0.0195
whereas data measured by the gas-phase recirculation method AAD (%) 2.782 0.598 0.729 0.538 1.254
are obtained by recording experimental data with a high accuracy
directly. The gas-phase recirculation method results are larger than
those of the semi-flow-type method. The samples of the semi-
f2
flow-type method were analyzed by the gravimetric method with T ¼ 313:15 K ln ¼ 0:0154pCO2 þ 1:7686 ð14Þ
a complicated analysis procedure, and large errors. x2

3.2. Prediction models for CO2-DES VLE f2

T ¼ 328:15 K ln ¼ 0:0145pCO2 þ 1:8424 ð15Þ
x2
The results derived from fitting the experimental data using
3.2.1. K-K model Eqs. (11)–(15) and the relative errors (<0.2%) between the calcu-
In general, the K-K model is applicable to correlate gas- lated data of the K-K model and the experimental data are shown
solubility data over a wide concentration range. Parameters of in Fig. 6. The solubility data are correlated with the K-K model,
the K-K model can be evaluated from the regression, and deter- with average relative deviations of 0.05%. This model can predict
mined by the least-square algorithm. The parameter results are the solubility of CO2 in DES, broaden the scope of Henry’s law,
shown in Table 4 and equations from the correlation of gas- increase the accuracy for gas solubility, and contribute to the selec-
solubility data are shown in Eqs. (11)–(15). Henry constants tion of an appropriate solvent.
increase with temperature for a given solvent owing to the
decrease in CO2 solubility with increasing temperature.
3.2.2. The PR equation of state
f The parameters of the PR EOS that were derived from the fitting
T ¼ 288:15 K ln 2 ¼ 0:0176pCO2 þ 1:3178 ð11Þ
x2 experimental data are shown in Table 5. The results that were cal-
culated from the PR EOS, a comparison with the experimental val-
f2 ues, and the relative errors are shown in Fig. 7.
T ¼ 298:15 K ln ¼ 0:0167pCO2 þ 1:4984 ð12Þ
x2 Fig. 7 shows that the results from the PR equation are consistent
with the experimental values for the CO2-DES system, with an
f2 average error of 1.14%. Therefore, it is appropriate to use the
T ¼ 308:15 K ln ¼ 0:0158pCO2 þ 1:6813 ð13Þ
x2 equation-of-state method to calculate the VLE data of the CO2-
DES system.
Table 4
Relevant parameters for K–K model and relative deviations.
3.2.3. Molecular simulation
T (K) 288.15 298.15 308.15 313.15 318.15
Henry constants of the CO2-DES system were compared with
K0 (MPa) 3.74 4.47 5.37 5.86 6.31
V 2 (m3mol1) 42.16 41.40 40.48 40.09 39.56 those of the CO2-DEC [27] and CO2-DMC [38] systems, as shown
AAD (%) 0.083 0.023 0.052 0.037 0.095 in Fig. 8. The values of Henry constant increase as: DES < -
Pn n o DEC < DMC at the same temperature. For example, the values of
jxexp xcal j
AAD ð%Þ ¼ 100
k¼1 .
n xexp k Henry constant for carbonates increase as 298.15 K: DES
 H. Li et al. / Applied Energy 200 (2017) 119–131 125

4 the structure formed by the solvent molecule is more unstable, CO2

288.15K 298.15K interacts more easily with the solvent molecule, and CO2 absorp-
308.15K 313.15K
3 tion by the solvent is better. The interaction energy between the
318.15K
PR EOS solvent and the CO2 molecules is the energy released to form inter-
molecular bonds and it is smaller, which indicates that the system
p/MPa

2
formed by the solvent and CO2 molecules is more stable, CO2 inter-
acts more strongly with solvent molecules, and CO2 absorption by
1 the solvent is better. Two kinds of interaction energies were used
to evaluate the solvent capacity for capturing CO2. The quantum
0
5.0 chemical calculation at the B3LYP/6-311++G⁄⁄ level with Gaussian
09 software was used to calculate the interaction energy between
2.5 carbonate molecules and that of the carbonate molecules with the
CO2 molecule. Optimized geometries of the carbonates are shown
p/p(%)

in Fig. 9. Fig. 10 shows the interaction energy of the carbonates.

0.0
Fig. 11 shows the interaction energy between the carbonates and
CO2, respectively. The interaction energies are listed in Table 6.
-2.5 A negative interaction energy in Table 6 denotes the energy
released to form molecular bonds, and its absolute value, which
-5.0 is the broken bond energy between the carbonate molecules, is
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 applied to evaluate the intermolecular interaction of the carbon-
xCO2 ates. The absolute values of the interaction energy of the carbon-
ates decrease as follows: DMC-DMC (39.4874 kJmol1) > DEC-
Fig. 7. Comparison of calculated and experimental data from the PR EOS model and
DEC (31.8230 kJmol1) > DES-DES (21.0300 kJmol1), which
relative deviations.
states that the structure that is formed by DES molecules is broken
more easily than the DEC and the DMC, and the DES molecules
combine better with the CO2 molecule. The values of the interac-
8 DES tion energy of carbonates with CO2 increase as: DMC-CO2
DEC (7.6671 kJmol1) > DEC-CO2 (8.0331 kJmol1) > DES-CO2
DMC
(9.1441 kJmol1), which states that the DES and CO2 molecule
7
interaction is more stable than the DEC and DMC and the interac-
tion force between the DES and CO2 molecules is stronger than the
6 DEC and DMC. The CO2 absorption capacity of the DES is better
H/MPa

than the DEC and DMC in terms of the absorbed energy between
carbonates and the released energy of CO2 with carbonates.
5
The relationship between Henry constant at 298.15 K and the
interaction energy between the carbonates and of CO2 with car-
4 bonates is shown in Fig. 12. With increasing Henry constant, the
absorbed energy broken between the carbonate molecules
3
increases, which also indicates that the broken energy is larger
280 290 300 310 320 and that the effect of solvent capture of CO2 worsens. The released
T/K energy formed by the solvent and CO2 molecules increases, which
indicates that the released energy is larger and the effect of solvent
Fig. 8. Comparison of Henry constants of DES with DEC and DMC. capture of CO2 is worse.

3.3. CO2-DES continuous absorption-desorption process

(4.4745 MPa) < DEC (5.6907 MPa) < DMC (6.2823 MPa). Therefore,
in term of CO2 capture capacity, DES performs best followed by
DEC and then DMC.
Two parameters are used to evaluate the solvent capacity for
CO2 capture: the interaction energy of the solvent molecules and
that between the solvent molecule and CO2. The interaction energy
of the solvent molecules is the absorbed energy required to break
intermolecular bonds. This energy is smaller, which indicates that
3.3.1. Impact of liquid-gas ratio on CO2 absorptivity
The pressure and temperature in the absorber and desorber
were 3.10 MPa and 292.65 K, and atmospheric pressure and
353.25 K, respectively. A variation was carried out as follows. The
rate of solvent circulation was relatively easy to change. Therefore,
the gas flow rate was set at 15 NL/min and the liquid-gas ratio was

DMC DEC DES

Fig. 9. Optimized geometries of isolated DMC, DEC, and DES at B3LYP/6-31++g** level.
126 H. Li et al. / Applied Energy 200 (2017) 119–131

DMC-DMC DEC-DEC DES-DES

Fig. 10. Optimized geometries of DMC-DMC, DEC-DEC, and DES-DES at B3LYP/6-31++g** level.

DMC-CO2 DEC-CO2 DES-CO2

Fig. 11. Optimized geometries of DMC-CO2, DEC-CO2, and DES-CO2 at B3LYP/6-31++g** level.

Table 6
Interaction energy between carbonates and of CO2 with carbonates.
100
System DHcal (kJmol1) System DHcal (kJmol1) (a)
DMC-DMC 39.4874 DMC-CO2 7.6671 90
DEC-DEC 31.8230 DEC-CO2 8.0331
/100%

DES-DES 21.0300 DES-CO2 9.1441

80
CO2

70
DES DEC DMC
DMC-DMC 60
40
DEC-DEC 10 (b)
H/kJ · mol -1

DES-DES
8
GJ/tonCO2

30
6

20 4

DMC-CO2 18
-7 (c)
14
kgSolvent/tonCO

DEC-CO2
H/kJ · mol -1

9
-8 DES-CO2
5

-9
0.1

0.0
-10 0 1 2 3 4 5 6 7 8
4.5 5.0 5.5 6.0 6.5
L/V
H/MPa
Fig. 13. Impact of liquid–gas ratio on CO2 absorptivity (a), energy consumption (b)
Fig. 12. Relationship between Henry constant at 298.15 K and interaction energy and solvent loss (c) (points denote experimental data and lines denote simulated
between carbonates and of CO2 with carbonates. data).
 H. Li et al. / Applied Energy 200 (2017) 119–131 127

100 98
(a) (a)
95 96

/100%
/100%

90
94

CO2
CO2

85 DES DEC DEC

92
DES DEC DMC
80 2.0
(b)

(desorption solvent)
4
(b) 1.5

xCO2/100%
GJ/tonCO2

1.0
3
0.5

2 10

(c)
8

GJ/tonCO2
9
(c) 5
7
kgSolvent/ton CO

3
4

2 0
8 (d)
0.1
kgSolvent/ton CO
6

0.0 4
280 290 300 310
2
Tabsorption /K
0.02
Fig. 14. Impact of absorption temperature on CO2 absorptivity (a), energy
0.00
consumption (b) and solvent loss (c) (points denote experimental data and lines
denote simulated data). 300 330 360 390 420 450 480
Tdesorption /K

varied by adjusting the solvent flow rate. The impact of liquid-gas
ratio on CO2 absorptivity, energy consumption, and solvent loss is
shown in Fig. 13. The experimental results agree well with the sim-
ulated results. When the liquid-gas ratio is less than 1.337, the CO2
absorptivity increases rapidly with increasing liquid-gas ratio. As
the liquid-gas ratio increases, the solvent quantity increases. This
causes the sprinkle density, contact area between the gas and liq-
uid, and the driving force for mass transfer in the absorber to
increase, which results in an increased CO2 absorptivity. When
the liquid-gas ratio is greater than 2.107, the response flattens
and the CO2 absorptivity is maintained at 96.50%, and the absor-
ber reaches CO2-DES equilibrium, which implies that an increase in
CO2 absorptivity does not depend only on an increase in DES flow.
The solvent quantity increases with increasing liquid-gas ratios,
and the heat and cooling duty increase at the same absorption
and desorption temperature. Therefore, the energy consumption
for capture increases with increasing liquid-gas ratios, whereas
the range of solvent loss is 0.024–0.061 kg solvent/ton CO2. The
solvent loss is almost unchanged for the DES high boiling point
and low volatility. Therefore, in order to ensure the CO2 absorption
capacity exceeds 95%, the energy consumption for capture and the
solvent loss reach minimum levels and when the liquid-gas ratio is
1.337. The optimal liquid-gas ratio is 1.337 for the CO2-DES system.
The optimal liquid-gas ratio is 1.475 for the CO2-DEC system
[32] and 1.556 for the CO2-DMC system [27]. The optimal liquid-
gas ratios increase as follows: DES (1.337) < DEC (1.475) < DMC
(1.556). Because of the higher CO2 absorption capacity of the
DES, a smaller quantity of DES deals with the same CO2 quantity,
and its optimal liquid-gas ratio is lower.
Fig. 15. Impact of desorption temperature on CO2 absorptivity (a), CO2 concentra-
tion of desorption solvent (b), energy consumption (c) and solvent loss (d) (points
denote experimental data and lines denote simulated data).
The DEC [32] and DMC [27] results are listed in Fig. 13. By com-
paring the results from the three solvents, it can be shown that at
the same liquid-gas ratio, the decreasing trend in CO2 absorptivity
is DES > DEC > DMC; the energy consumption decreases as: DES
(boiling point: 490.85 K) > DEC (398.95 K) > DMC (363.22 K); the
solvent loss increases as: DES < DEC < DMC, and DES has little sol-
vent loss with a high boiling point and low volatility.
3.3.2. Impact of absorption temperature on CO2 absorptivity
The gas flow rate, liquid–gas ratio, pressure, and temperature in
the absorber were set at 15 NL/min, 1.337, 3.10 MPa, and 354.75 K,
respectively. The absorption temperature was regulated by the
feed temperature of the circulated solvent. The impact of absorp-
tion temperature on CO2 absorptivity, energy consumption, and
solvent loss is shown in Fig. 14. The absorptivity decreases with
increasing absorption temperature and the experimental results
agree well with the simulated results; the energy consumption
firstly decreases with increasing absorption temperature, then
increases slightly when the absorption temperature is 296.15 K.
The range of solvent loss is 0.012–0.074 kg solvent/ton CO2, and
the solvent loss remains unchanged with increasing absorption
temperature. To achieve significant economic benefits and to
ensure that the CO2 absorption capacity exceeds 95%, the temper-
ature range of 291.15–293.15 K was considered appropriately.
128 H. Li et al. / Applied Energy 200 (2017) 119–131

100 temperature, the CO2 absorptivity of the DES is greater than that
(a) of the DEC and DMC and the energy consumption of the DES is
98 higher than that of the DEC and DMC because DES has a high boil-
ing point. The DES solvent loss is much lower than that of the DEC
/100%

96
and DMC.
CO2

94
3.3.3. Impact of desorption temperature on CO2 absorptivity
92 The gas flow rate, liquid-gas ratio, pressure, and temperature in
DES DEC DMC the absorber were set at 15 NL/min, 1.337, 3.10 MPa, and 293.25 K,
90 respectively. The desorption temperature was regulated by a heat-
0.18 (b) ing jacket power outside the desorber. The impact of desorption
temperature on CO2 absorptivity, CO2 concentration of desorption
solvent, energy consumption, and solvent loss is shown in Fig. 15.
GJ/tonCO2

0.16 With increasing desorption temperature, the CO2 concentration of

the desorption solvent decreases, which favors CO2 capture; the
CO2 absorptivity increases and the experimental results agree well
0.14
with the simulated results; the energy consumption increases as
the heating jacket power increases; the range of solvent loss is
0.12 0.028–0.029 kg solvent/ton CO2, i.e., the solvent loss is almost
24 unchanged. A temperature range of 433.15–443.15 K is considered
20 (c) appropriate to achieve a CO2 absorption capacity that exceeds 95%
16 and a small energy consumption.
kgSolvent/tonCO

The optimal desorption temperature is 353.15–358.15 K for the

4.0 CO2-DEC system [32] and 333.15–338.15 K for the CO2-DMC sys-
3.5 tem [27]. The optimal temperature decreases as follows: DES
3.0 (433.15–443.15 K) > DEC (353.15–358.15 K) > DMC (333.15–
0.05 338.15 K). Because the boiling point of DES is higher than that of
0.04 the DEC and DMC, solvent regeneration of DES requires a higher
0.03 temperature.
0.00 0.10 0.20 0.30 0.40
The DEC [32] and DMC [27] results are shown in Fig. 15. By
comparing the results from the three solvents, it can be seen that
x N2 /(molN2 /molG)
when the desorption temperature is high, the CO2 concentration
of the desorption solvent is low and the CO2 absorptivity is high.
Fig. 16. Impact of N2 flow on CO2 absorptivity (a), energy consumption (b) and
solvent loss (c) (points denote experimental data and lines denote simulated data). When the desorption temperature is low, the DES exhibits no
advantage over the DEC and DMC. Because the DES boiling point
is higher than that of DEC and DMC, the energy consumption of
The optimal absorption temperature is 288.15–293.15 K for the DES is higher than that of DEC and DMC. Because of the low volatil-
CO2-DEC system [32] and 288.15–293.15 K for the CO2-DMC sys- ity of the DES, it exhibits little solvent loss, much less than that of
tem [27]. The optimal temperature decreases as follows: DES the DEC and DMC.
(291.15–295.15 K) > DEC (288.15–293.15 K)  DMC (288.15–
293.15 K). Because the CO2 absorption capacity of DES is higher 3.3.4. Impact of N2 flow on CO2 absorptivity
than that of the DEC and DMC, the absorption temperature does The thermal-desorption process requires energy to regenerate
not need to be too low for DES to be effective in absorbing CO2. the solvent. To reduce the energy consumption and associated cost,
The DEC [32] and DMC [27] results are shown in Fig. 14. A com- N2 gas-stripping desorption was investigated for the optimized
parison of the three solvents shows that at the same absorption conditions described above. The gas flow rate, liquid-gas ratio,

Table 7
Calculated results for absorption and thermal-desorption process of CO2-DES, CO2-DEC, and CO2-DMC.

Solvents L/V CO2 absorptivity Energy consumption (GJ/ton CO2) Solvent loss (kg System cost (Yuan RMBa/ton CO2)
(%) solvent/ton CO2)
DES 1.337 96.49 Cooling 3.842 49.94% 0.028 Cooling 105.0 32.84%
Heat 3.780 49.13% Heat 202.2 63.24%
Pump power 0.071 0.93% Pump power 11.83 3.70%
Solvent loss 0.70 0.22%
Total 7.694 Total 319.7
DEC 1.48 95.95 Cooling 1.713 49.84% 2.680 Cooling 46.82 28.58%
Heat 1.671 48.61% Heat 89.34 54.54%
Pump power 0.053 1.55% Pump power 8.89 5.42%
Solvent loss 18.76 11.45%
Total 3.437 Total 163.8
DMC 1.56 94.66 Cooling 0.854 49.57% 6.113 Cooling 23.33 21.46%
Heat 0.827 48.03% Heat 44.24 40.70%
Pump power 0.041 2.10% Pump power 6.89 6.34%
Solvent loss 34.23 31.49%
Total 1.722 Total 108.7
a
1 Yuan RMB = 0.1476 USD.
 H. Li et al. / Applied Energy 200 (2017) 119–131 129

pressure, and temperature in the absorber were set at 15 NL/min,
1.337, 3.10 MPa, and 293.45 K, respectively. The pressure in the
desorber was atmospheric pressure, and the temperature in the
desorber was 290.95 K. The impact of N2 flow on CO2 absorptivity,
energy consumption, and solvent loss is shown in Fig. 16. The N2-
feed gas ratio (mol N2/mol G) was used to ensure a quantitative
desorber effect with a 15 NL/min gas flow rate. With increasing
N2 flow, the CO2 concentration in the desorption solvent decreases.
The best effect that N2 gas-stripping desorption can achieve is that
the CO2 concentration in the desorption solvent is zero and that the
DES concentration into the absorber is nearly 100%, when the CO2
absorptivity is 98.34%. When the N2 flow is less than 1 NL/min, the
energy consumption decreases and when the N2 flow exceeds
1 NL/min, the energy consumption increases. The impact of N2 flow
on solvent loss is weak. In summary, to ensure CO2 absorptivity,
the optimum N2 flow should be 0.5 NL/min.
The DEC [32] and DMC [27] results are shown in Fig. 16. A com-
parison with three solvent results shows that for the same N2 flow,
the CO2 absorptivities decrease as: DES > DEC > DMC, the energy
consumption decreases as: DES > DEC > DMC, and the solvent
losses increase as: DES < DEC < DMC.
3.3.5. Thermal desorption versus gas-stripping desorption
The system energy consumption, solvent loss, and capture cost
were calculated to compare the operating costs for thermal desorp-
tion and gas-stripping desorption. The cost results for thermal des-
orption and gas-stripping desorption are given in Tables 7 and 8,
respectively.
A comparison of the CO2-DES results in Table 7 with those in
Table 8 shows that the cooling and heating energy consumption
for the thermal desorption option account for more than 99% of
the total operating cost. Gas-stripping desorption requires no heat-
ing energy and the total energy consumption (0.164 GJ/ton CO2) is
significantly lower than that for thermal desorption (7.694 GJ/ton
CO2, 319.7 Yuan RMB) and results in a lower overall capture cost
(37.88 Yuan RMB). Because of the high boiling point and low

Table 8
Calculated results for absorption and gas-stripping desorption of CO2-DES, CO2-DEC, and CO2-DMC.

Solvents L/V CO2 absorptivity/% Energy consumption (GJ/ton CO2) Solvent loss (kg solvent/ton CO2) System cost (Yuan RMBa/ton CO2)
DES 1.337 96.42 Cooling 0.095 57.93% 0.038 Cooling 2.60 6.86%
Pump power 0.069 42.07% Pump power 11.50 30.36%
Solvent loss 0.95 2.51%
N2 quantity 22.38 60.27%
Total 0.164 Total 37.88
DEC 1.48 96.42 Cooling 0.102 66.23% 3.557 Cooling 3.82 7.49%
Pump power 0.052 33.77% Pump power 8.70 17.05%
Solvent loss 24.90 48.80%
N2 quantity 13.60 26.66%
Total 0.154 Total 51.02
DMC 1.56 96.04 Cooling 0.090 68.70% 14.84 Cooling 1.47 1.62%
Pump power 0.041 31.30% Pump power 6.77 4.42%
Solvent loss 87.00 56.87%
N2 quantity 56.74 37.09%
Total 0.131 Total 153.0
a
1 Yuan RMB = 0.1476 USD.

Liq-add
P1
M2
H4
C1
C2

H2
F1 F2

H1
M1 T
Gas-in H3
Gas-out
F3

Fig. 17. Schematic diagram of novel desorption process: T: absorber; C1, C2: compressors; H1, H2: heat exchangers; H3, H4: condenser; F1–3: flash tanks; M1, M2: mixers;
P1, P2: pumps.
130 H. Li et al. / Applied Energy 200 (2017) 119–131

Table 9
Calculated results for new continuous cycle of CO2-DES, CO2-DEC, and CO2-DMC.

Solvents CO2 absorptivity/% Energy consumption (GJ/ton CO2) Solvent loss (kg solvent/ton CO2) System cost (Yuan RMBa/ton CO2)
DES 90 Cooling 0.201 59.82% 0.552 Cooling 5.49 16.38%
Heat 0.073 21.73% Heat 3.90 11.63%
Pump power 0.062 18.45% Pump power 10.33 30.82%
Total 0.336 Solvent loss 13.80 41.17%
Total 33.52
DEC 90 Cooling 0.543 50.70% 1.147 Cooling 14.83 12.70%
Heat 0 0 Pump power 87.95 75.29%
Pump power 0.528 49.30% Solvent loss 14.03 12.01%
Total 1.071 Total 116.81
DMC 90 Cooling 0.509 43.62% 7.954 Cooling 13.90 8.27%
Heat 0 0 Pump power 109.65 65.23%
Pump power 0.658 56.38% Solvent loss 44.54 26.50%
Total 1.167 Total 168.09
a
1 Yuan RMB = 0.1476 USD.

volatility of DES, solvent losses decrease in gas-stripping desorp-
tion but more N2 flow is required. Gas-stripping desorption in
the CO2-DES absorption-desorption system has obvious advan-
tages over thermal desorption.
A comparison of the CO2-DES results with those of CO2-DEC [32]
and CO2-DMC [27] in Table 7 shows that the DMC solvent loss is
higher than that of DEC and DES to ensure that the CO2 absorptivity
is higher than 95% with the required liquid-gas ratio. The energy
consumption and total cost increase as: DMC < DEC < DES, because
a high desorption temperature results from the solvents’ high boil-
ing point. DMC is the best option for thermal desorption, and is
superior to DES and DEC.
A comparison of CO2-DES results with those of CO2-DEC [32]
and CO2-DMC [27] in Table 8 shows that the solvent loss and sys-
tem cost increase as follows: DES < DEC < DMC. DES is the best
option for N2 gas-stripping desorption, and is superior to DEC
and DMC.
3.4. Novel CO2-DES absorption-desorption process
A novel process should be explored to reduce capture costs. The
desorption process was modified by applying compression and
condensation to desorb the absorption liquid, and the desorber,
product scrubber, and desorption gas scrubber were removed,
which simplifies the process. A schematic of the process is pre-
sented in Fig. 17. The pressure, temperature, and liquid–gas ratio
in the absorber were 3.10 MPa, 293.15 K, 1.337, respectively, and
the specific process was described previously [27,32]. The process
was simulated using Aspen Plus 2006 with the results as shown in
Table 9.
A comparison of Tables 7 and 8 shows that the energy con-
sumption for DES (0.336 GJ/ton CO2) is less than that of the
thermal-desorption process (7.694 GJ/ton CO2) but slightly greater
than that for gas-stripping desorption (0.164 GJ/ton CO2). Solvent
losses (0.552 kg solvent/ton CO2) were greater than that of gas-
stripping desorption (0.038 kg solvent/ton CO2) and that of ther-
mal desorption (0.028 kg solvent/ton CO2). However, the CO2
absorptivity is slightly less than that for the other two processes
and the operating cost (33.52 Yuan RMB) is lower than that for
the thermal desorption (319.7 Yuan RMB) and gas-stripping des-
orption (37.88 Yuan RMB). Other advantages of this process
include its simplicity, ease of operation, and its relatively low
investment cost.
The DEC [32] and DMC [27] results as simulated by this process
are listed in Table 9. A comparison of the results using these three
solvents shows that the solvent loss, system energy consumption,
and capture costs increase as follows: DES < DEC < DMC. DES is the
best option for this process, and is superior to DEC and DMC.
4. Conclusions
The gas-phase recirculation method was used to determine the
VLE data for the CO2-DES system at 288.15, 298.15, 308.15, 313.15,
and 318.15 K and a pressure up to 2.99 MPa. The results were mod-
eled by the K-K model with relative errors of 0.05% and the PR EOS
had relative errors of 1.14%. These models were good gas-solubility
prediction models for the CO2-DES system.
A comparison of the Henry constants of DES with those of DEC
and DMC shows that the values increase as: DES < DEC < DMC at
the same temperature. The absorbed energy to break bonds
between the carbonate molecules increases as follows: DES-DES
(21.0300 kJmol1) < DEC-DEC (31.8230 kJmol1) < DMC-DMC
(39.4874 kJmol1) and the released energy to form bonds between
the carbonate and CO2 molecule increases as: DES-CO2
(9.1441 kJmol1) < DEC-CO2 (8.0331 kJmol1) < DMC-CO2
1
(7.6671 kJmol ), which shows that the CO2 absorption capacity
of DES is better than DEC and DMC.
A continuous absorption-desorption experiment for the CO2-
DES system was designed to test the stability and to study the opti-
mum operating conditions. These conditions were found to be: a
liquid-gas ratio of 1.337 and an absorber temperature range from
291.15 to 293.15 K. If the thermal-desorption process is applied,
the optimum desorber temperature range is 433.15–443.15 K. If
gas-stripping desorption is applied, the optimum N2 flow is
0.5 NL/min. A comparison of the two desorption processes shows
that gas-stripping desorption requires no heating energy, its total
energy consumption is significantly lower than for the thermal
desorption, and it results in a lower overall capture cost. A compar-
ison of CO2-DES results with those of CO2-DEC and CO2-DMC, indi-
cates that DMC (108.7 Yuan RMB) is the best option and is superior
to DES (319.7 Yuan RMB) and DEC (163.8 Yuan RMB) for thermal
desorption; DES (37.88 Yuan RMB) is the best option and is supe-
rior to DEC (51.02 Yuan RMB) and DMC (153.0 Yuan RMB) for N2
gas-stripping desorption.
It was suggested that to reduce operating costs, the CO2-DES
continuous absorption-desorption process may be improved by
removing the desorber, product scrubber, and desorption gas
scrubber, and applying compression and condensation to desorb
the absorption liquid. Simulation results showed that, for such a
process, the total operating cost of this novel system was lower
than that for thermal desorption and gas-stripping desorption.
Moreover, the novel method has the advantages of being a simple
 H. Li et al. / Applied Energy 200 (2017) 119–131
process and is easy to operate. A comparison of CO2-DES results
with those of CO2-DEC and CO2-DMC indicates that the solvent
losses, system energy consumptions, and the capture costs
increase as follows: DES (0.552 kg solvent/ton CO2, 0.336 GJ/ton
CO2 and 33.52 Yuan RMB) < DEC (1.147 kg solvent/ton CO2,
1.071 GJ/ton CO2 and 116.81 Yuan RMB) < DMC (7.954 kg solvent/
ton CO2, 1.167 GJ/ton CO2 and 168.09 Yuan RMB). DES is the best
option and is superior to DEC and DMC for this process.
Acknowledgments
This study was supported by the National Key Technology Sup-
port Program of China (No. 2015BAC04B00), and Shenzhen Science
and Technology Plan project of China (JCYJ20140902110354253,
JCYJ20160608165926763). We thank the editors and anonymous
reviewers for their thorough reviews and constructive comments.
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