Review On Oxy Combustion

Journal of Environmental Chemical Engineering 9 (2021) 105777
Contents lists available at ScienceDirect
Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece
Review on principles, recent progress, and future challenges for oxy-fuel

combustion CO2 capture using compression and purification unit
Esmaeil Koohestanian *, Farhad Shahraki
Department of Chemical Engineering, University of Sistan and Baluchestan, Zahedan, Iran
A R T I C L E I N F O A B S T R A C T
Keywords: The emission of anthropogenic carbon dioxide (CO2) as a result of fossil fuel burning is regarded as a leading
CO2 capture cause of global warming and environmental problems. An efficient method to capture CO2 from flue gases is oxy-
Oxy-fuel combustion fuel combustion. CO2 compression and purification unit (CO2CPU) is a promising process to capture CO2 from
CO2CPU
oxy-fuel combustion flue gases. However, the widespread implementation of this method is encountered with
Greenhouse gas
Global warming
different techno-economical and legal challenges. The present study aims to review the principles and latest
Review advances of CO2CPU process as well as the challenges this process may encounter in the future. The CO2CPU
system is introduced and the latest research on the optimization and dynamic investigation of this process are
reviewed. In addition, relevant standards and specifications of CO2 product as well as the effect of impurity are
collected. Finally, a summary of the future challenges and research directions is presented.
2018, annual CO2 production reached 33.5 Gt and have grown by an

average of 2.4% per year. It is forecasted that due to increase CO2 the
1. Introduction mean worldwide temperature increase to around 3.2 ◦ C, by 2100, and
hence, significantly affecting the earth and human activities [7]. The
During the period from 1760 to 1840, especially from the beginning contribution of the primary sources of CO2 emission which was obtained
of the Industrial Revolution, anthropogenic activities increased the from the data extracted from IEA in 2018 is presented in Fig. 1 [8]. As
emission of greenhouse gases, particularly CO2, from 280 ppm to illustrated in Fig. 1 electricity and heat production, by accounting for
370 ppm [1]. During the same period, the average worldwide temper 42% of the globally emitted CO2, is the main cause of CO2 emission.
ature experienced a rise in the range of 0.6 ◦ C and 1 ◦ C [2]. The accu Also, more than 65% of CO2 emission are resulted from combusting a
mulation of greenhouse gases in the atmosphere has resulted in a huge quantity of coal and natural gases, which show the significant
gradual increase in the average Earth temperature which has been called impact of these processes on climate change.
global warming and turned into a widespread concern over the recent To reduce CO2 emissions, there are different approaches such as
years [3]. Global warming as a great threat to life on earth will lead to expanding renewable energies such as solar and wind energies [9], fuel
some problems such as sea level rise which is associated with the loss of switching from coal to natural gas [10], applying regulations on the total
coastal area, and sever weather conditions such as drought, hurricane, CO2 emission [11], utilizing CO2 as a raw material [12], enhancing plant
and flood [4]. CO2 was the most produced flue gases from industrial efficiency to more energy saving [13], and applying carbon capture and
emissions, around 33% of which was produced as a result of burning storage (CCS) approach [14]. However, due to the great world energy
carbon-intensive fossil fuels such as coal and oil [5]. As the scientists are demand and based on the fact that renewable energies still need more
aware of the significant effect of this pollutant on global warming, CO2 work to make them economically competitive to the fossil fuel price,
emission became the most serious environmental issue in the 21st cen more need is felt for the continuous use of reasonable and sustainable
tury [6]. Accordingly, in the latest global agreement to combat climate fossil fuels with decreased environmental consequences which requires
change (the Paris Agreement enacted in 2016), the United Nations the integration of the CCS technologies [15]. CCS does not aim to
Framework Convention on Climate Change (UNFCCC) member states decrease the formation of CO2, rather to capture it from emissions and
committed to reduce CO2 emissions, although this pollutant is still store it under the earth’s surface, for example in unused oil and gas
increasingly generated throughout the world. Based on a report by the fields, and deep saline formations [16]. Capturing CO2 from the primary
International Energy Agency (IEA), due to higher energy demand in
* Corresponding author.
E-mail addresses: [email protected] (E. Koohestanian), [email protected] (F. Shahraki).
https://doi.org/10.1016/j.jece.2021.105777
Received 9 January 2021; Received in revised form 1 May 2021; Accepted 28 May 2021
Available online 1 June 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
E. Koohestanian and F. Shahraki Journal of Environmental Chemical Engineering 9 (2021) 105777
Nomenclature Greek letters

α thermal diffusivity, m2/s
A heat-transfer area µ dynamic viscosity, Pa s
C corrosion allowance, mm ω Pitzer acentric factor
CCB installed cost of cold-box, US$ ρ density, kg/m3
Ccomp investment costs of compressor ρv vapor density, kg/m3
CP specific heat capacity, J/(kg K) τ wall thickness, mm
Cvol cost per unit volume for the aluminium plate-fin heat
exchangers, 104 US$/m3 Abbreviations
D diameter ASU air separation unit
E joint efficiency CCS carbon capture and storage
fm total module factor CES clean energy systems
k thermal conductivity, W/(m K) CLC chemical looping combustion
K compression ratio CPU compression and purification unit
kij the experimental temperature-dependent binary CW cooling water
parameters DCC direct contact condensation
ṁ mass flow rate (kg/s) EOR enhanced oil recovery
N number of stages EOS equation of state
P pressure, bar IEA International Energy Agency
PC critical pressure, bar IEAGHG International Energy Agency Greenhouse Gas
Pin inlet pressure, bar IGCC integrated gasification combined cycles
Pout outlet pressure, bar MEA monoethanolamine
Q vapor volumetric flowrate in m3/s MOP maximum operating pressure
R universal gas constant, 8314 J/(kmol K) MSC multi-stages compressor
rp cost ratio for operating pressures NGCC natural gas-fired combined cycle
S maximum allowable stress, bar NGF natural gas fuel
t ton NOX nitrogen oxide
th half full holdup time, s PCF pulverized coal fuel
T absolute temperature, K PFD process flow diagram
TC critical temperature, K PI controller proportional-integral controller
U overall heat-transfer coefficient, W/m2K PVT pressure-volume-temperature
V volume, m3 PR Peng-Robinson
VDrum volume of drum, m3 RGA relative gain array
Vmax maximum vapor velocity, m/s RSM response surface methodology
VCB volume of a single-train cold-box, m3 SCOC-CC semi-closed oxy-fuel combustion combined cycle
x molar fraction SOX sulfur oxide
SRK Soave-Redlich-Kwong
UNFCCC United Nations Framework Convention on Climate Change
also to review the principles, latest advances, bottlenecks of this process

and the challenges it may face in the future. To that end, the Section 2
provides some information about the three main CO2 capture technol
ogies with an emphasis on the oxy-fuel combustion. The next section,
describes the oxy-fuel combustion and Section 4, presents some details
on CO2 quality requirements and product’s characteristics. The next
section introduces CO2CPU process, its simulation, and its thermody
namic equation of state. Main results obtained from CO2CPU sensitivity
analysis and optimization are discussed in Section 6. Dynamic modeling
and simulation of this process are explained in Section 7 and the con
clusions and the future research needed to be done on the CO2CPU
process are summarized in Section 8. Research conducted on CO2CPU
process are presented in Fig. 2.
Fig. 1. The contributions of the primary source of CO2 emission.
source is the most crucial step because it represents 70–90% of the total
operating costs [17]. Therefore, the development of new carbon capture
techniques to minimize the current atmospheric CO2 level is so essential
for the continuous development of human civilization [18].
The present study aims to introduce the CO2CPU process as an
effective way in capturing CO2 from oxy-fuel combustion flue gases. It is
Fig. 2. Researches related to the CO2CPU process.
2
2. Carbon capture and storage 3. The oxy-fuel combustion
CCS is recognized as a critical technology and promising approach to This method is beneficial for most combustion systems because it
reduce the global emission of CO2 produced by large-scale fossil fuel only requires O2 during the combustion process. Presence of N2 not only
systems such as power plants [19]. This technology is applied to capture increases the formation of nitrogen oxide (NOX) as the major emission of
CO2 from primary sources such as power plants and transport for sta concern, but also decreases the thermal efficiency through lowering the
bilization using permanent storage in deep geological formations such as radiative heat transfer as well as, less heat can be transferred from the
saline formations or its conversion to stable products in a way that it is hot flue gases as more energy is wasted in heating N2 and more energy is
omitted from the atmosphere [20]. Therefore, it is known as the most carried out via the flue gases [61]. Several oxy-fuel industrial processes
effective approach over the short term to capture and store major part of have been successfully operated worldwide, in which the flue gas stream
CO2 produced by industries. CO2 can be also used in EOR or as a raw with 90% of CO2 (on dry base) was generally achieved [62].
material or working fluid in low-temperature power cycle. However, The optimum O2 concentration for oxy-fuel application is usually
large-scale deployment of the CCS is encountered with various barriers about 97% mol [63], but due to power consumption increases sharply at
and challenges including economic factors such as high energy penalties higher purities, most works adopt 95% mol [64]. However, the exact
and costs for the capture and compression of CO2, lack of suitable inlet O2 purity depends on the fuel properties and the boiler design [65].
long-term storage sites, and the applicable environmental legislation Using O2 instead of air in combustion chamber boosts combustion effi
[16]. ciency [66], which decreases fuel consumption and produces a high CO2
Depending on gas stream conditions such as temperature, pressure, concentration stream (more than 80% vol.) which enable easier purifi
concentration of CO2 in flue gases, and the fuel type (solid or gas), the cation through mechanical separation using the difference in the
following three general methods are presented for CCS from primary condensing temperatures instead of the absorption-based separation
sources [21]: [67].
Using O2 instead of air in combustion chamber also increases the
- Pre-combustion which is usually applied in the integrated gasifica flame temperature about 3500 ◦ C which can damage the furnace [68].
tion combined cycles (IGCC) and implies the removal of CO2 from Therefore, in oxy-fuel combustion, high purity O2 is diluted by the
fuels before the combustion is completed via partial oxidation, recycled flue gases (wet or dry) to control the flame temperature in the
gasification or steam reforming process to give mainly a fuel gas or required level set by boiler metallurgical constraints [69]. In wet recy
synthesis gas (syngas) composed mainly of carbon monoxide and cling form, hot and humid flue gas recirculates to combustion chamber
hydrogen [22]. Syngas at the exit of desulphurization unit undergoes prior to the gas cleanup unit, where contains acid gases and ash parti
a water gas shift reactor to convert around 99% of CO to CO2 and H2 cles. Although this form of recirculation could avoid a significant
by addition of steam. The produced H2 can be fed to the power amount of energy losses, it is associated with several practical challenges
generation device as the working fuel after separated from CO2 [23]. like corrosion and erosion. Therefore, dry flue gas recirculation is rec
- Post-combustion that, by physical or chemical processes, captures ommended whereby, flue gas is recycled downstream of the gas cleanup
CO2 after combustion from flue gases; unit operations, such as particulate filters, flue gas desulfurization units,
- Oxy-fuel combustion, proposed by Abraham et al. [24], which uses and moisture condensers [70]. Thermos-physical properties of flue gas
recycled flue gas and high purity O2 (about 85–98%) obtained from in different conditions were shown in Fig. 5 [71].
air separation unit (ASU). Higher flame temperatures, especially those above 1700 K, increase
the NOX formation via oxidation of N2 [72]. However, it will not be the
Simplified block diagram of these three combustion CO2 capture main issue in the oxy-fuel combustion due to the low content of N2 in the
technology illustrated in Fig. 3 [25]. flue gas stream, as well as higher heat capacity of CO2, in comparison to
Among these three method, oxy-fuel combustion CO2 capture is N2 (as shown in Table 3) helps to control the flame temperatures and
considered as one of the most promising approach that both new and laminar flame speed [73]. The air-fuel combustion requires less dilution
existing power plants can use to achieve a near-zero CO2 emission [26]. and more fuel to achieve similar combustion characteristics [73].
Comparison between this three combustion methods are summarized in Furthermore, low N2 concentrations in oxy-fuel combustion facilitate
Table 1. the reduction of NO into N2 through the reverse Zeldovich mechanism
There are different refining processes such as adsorption, absorption, which is well known as predominant mechanism in NOx formation in
distillation, membrane, and algae-based uptake. However, the selection high-temperature combustion processes [74]. Therefore, the oxy-fuel
of an appropriate capture process is highly dependent on specific combustion has been broadly perceived as a promising approach to
discharge conditions such as temperature, flowrate, composition, and enhance the performance of fossil fuel combustion processes while
CO2 concentration in feed and final product [46]. Because of the un decrease the emission of environmental pollutants, especially CO2. In
certain performance and cost of the new process, most industries are addition, oxy-fuel combustion has more potential to integrate with the
inclined to use conventional processes [47]. Furthermore, they are more largest primary sources of CO2 emission such as power plants or cement
experienced in designing and operating these units, which are also industry [75].
highly available in markets [48]. Therefore, the CPU and absorption One of the significant differences between post- and oxy-fuel com
processes are more commonly-used in CO2 capturing. To the selection of bustion is the high cost of oxygen production which usually provided by
a suitable capture process, a review of the advantages and disadvantages cryogenic ASU which required high refrigeration duty [77] and it is
of these two method is necessary. Capturing carbon dioxide by these two expected 3–4% energy penalty for O2 production using ASU [78]. Since
processes is summarized and then compared in Table 2. the oxygen production in cryogenic ASU is costly (about 200 kWh/t O2
Fig. 4 represents the number of studies conducted in different years, at atmospheric pressure [79]), the oxy-fuel burning was initially used for
based on a Google Scholar search with the keywords CO2 compression high flame temperature applications such as glass, aluminum, iron, and
and purification unit and CO2CPU. This figure clearly shows that, steel factories where air-fuel combustion is not appropriate [80]. How
despite the rapid growth in the number of research published in this ever, attempts have been made over the last years through new method
field, the number of studies conducted is still limited and more research such as liquefied natural gas process [81] or new developed process, to
is required to be done in this area in the future. improve the performance of cryogenic ASU and decrease energy
3
Fig. 3. Block diagram of main combustion CO2 capture technology.
consumption to 139.0 kWh/t O2 in ASU [82]. Moreover, there are other heat to oxidize the fuel, such as hydrocarbons, rather than air between
methods, such as such as advanced ceramic membrane (145.0 kWh/t successive reaction loops along the two interconnected reactors: a fuel
O2), to produce O2 with the consumption of lower energy and capital reactor (reducer) and an air reactor also referred to as a combustor or
cost [83]. However, there are additional challenges in flux and O2 purity oxidizer) [85]. After the fuel oxidation in the fuel reactor, the reduced
in case of ceramic and polymeric membrane, respectively [45]. metal oxide is regenerated (re-oxidized) using air through exothermic
Another method which can be regarded as a variant of oxy-fuel oxidation reaction in the oxidizer reactor [86]. This successive process
combustion is chemical looping combustion (CLC) process. In this prevents dilution of combustion products (steam and CO2) with N2.
method, O2 is separated from air through fixing the O2 as a metal oxide Therefore, when hydrocarbons are used, combustion products are
(such as iron, copper, nickel,1 and manganese) without any need to mix generated and CO2 can easily be captured using steam condensation
combustion air and fuel [84]. The metal oxides are used to carry O2 and [87]. Therefore, the CLC technology may be considered as clean elec
tricity production in an IGCC power generation. In addition to power
generation, this method can be applied in the production of syngas [88],
hydrogen [89], and oxygen [90].
1
Nickel and nickel oxide are carcinogenic and should be avoided.
4
Table 1
Comparison of combustion technologies.
Combustion Pre-combustion Post-combustion Oxy-fuel combustion
technology
Efficiency penalty 7–10 [27] 8–12 [28] 7–11 [29]

(%)
Separation task CO2/H2 CO2/N2 O2/N2
Capture technology Chemical absorption such as alkanolamines [30] Chemical absorption such as amine scrubbing process CO2CPU process
Physical absorption such as ionic liquids [6] [30] CLC technology [37]
Membrane process using polymeric and ceramic Physical absorption such as ionic liquids [6] Cryogenic distillation [38]
membranes [23] Physical adsorption such as zeolites, activated carbon Physical adsorption such as zeolites
Physical adsorption such as zeolites, activated carbon [35], and metal-organic frameworks [31] and activated carbon
[31], alumina, and metal-organic frameworks [32] Membrane process using polymeric and ceramic Membrane process using polymeric
Cryogenic distillation [33] membranes and ceramic membranes
Gas hydrate crystallization [34] Gas hydrate crystallization [36] Ion transport membrane reactor [39]
Hybrid process Cryogenic distillation [33] Hybrid process
Hybrid process
Advantage Producing a carbon-free H2 based fuel [40] Causing minimum changes in the original Producing a highly concentrated CO2
configuration of the existing power plant [41] stream
Its maintenance does not stop the operation and can Low NOX production
be controlled [42] Increasing both the convective and
Mature technology radiative heat transfer [43]
Capturing can be applied without
additional material or solvent
Disadvantage/ Required additional cost for the syngas generation [44] High NOX production Requiring approximate pure O2
Limitation More costly in comparison with the other methods [45] Low CO2 purity in the flue gas leads to treatment of a
high volume of gas to separate CO2 [14]
Although CLC method can ignore ASU and acid gas removal unit and surplus oxygen must be injected to guarantee complete burning as what
hereby, decrease energy penalty compared to oxy- and pre-combustion happens in any air-fired furnace [91]. Moreover, low purity O2 decreases
(4.5%, compared with 7.1%, and 9.1%, respectively [37]), it suffers combustion reaction progress, leading to an unsteady and dark flame
from some limitations. Among them are the recycle rate of the solid [92].
between the reducer and an oxidizer and the average solids’ residence Capturing CO2 from oxy-fuel combustion flue gases is a highly effi
time in each reactor, physical strength and attrition resistance of oxygen cient, near zero-emission process, to which can be easily adapted a wide
carrier, oxygen-carrying capacity, the heat balance control, and tem range of furnace, utility boiler, fuel cell power plant [93], and com
perature control in each reactor. Furthermore, desulfurization of the fuel bustion systems such as both new and existing natural gas fuel (NGF)
is also necessary in order to avoid sulfidation of the metal oxide [47]. fired and pulverized coal fuel (PCF) fired power plants [94]. Comparison
Therefore, the ASU based on cryogenic distillation is still the most of these three combustion technologies (pre-, post-, and oxy-fuel com
suitable approach to produce large volumes of high purity O2 [45]. The bustion) integrated with a natural gas-fired combined cycle through
oxy-fuel combustion furnace is preferred to be operated with the lowest simulation analysis in Aspen Hysys® environment show that oxy-fuel
possible overall stoichiometry to decrease oxygen demand. However, combustion would provide both the power output and highest net
Table 2
Comparison of the CO2CPU and absorption processes.
Advantages Disadvantages
Chemical absorption based on • High CO2 purity [49] • High equipment corrosion [50]
alkanolamines • Suitable for retrofit of the traditional unit • Utilization of environment-unfriendly organic solvent (i.e., amines) [18]
• High recovery > 95% [17] • Additional material required as an inhibitor to control corrosion [51]
• Simple process • Increased corrosion with an increase in the amount of CO2 in feed stream
• Conventional process [52]
• Appropriate for flue gases with low CO2 concentration • Solvent degradation [53]
• Solvent loss [30]
• Decreased efficiency due to solvent pollution
• Foam formation
• Limitation in operating temperature [54]
• Heat stable salt formation in the presence of SOx and NOx [55]
• The high energy required for solvent regenerationa[56]
• Cooling unit required as pretreatment
• Large absorber volume
• Improper for oxy-fuel combustion flue gases [57]
• Production of hazardous byproduct [58]
• High viscosity [59]
• Highest operating and maintenance cost [60]
CO2CPU • Low corrosion • Ineffective for post-combustion flue gases
• High CO2 purity • The high energy required for compression and refrigeration unit
• Simple and cheap process • Dehydration process required as pretreatment
• Appropriate for flue gases with high CO2 • New process and needing more investigation
concentration
• Auto-refrigeration process
• No secondary pollution
a
About 80% of the total capture energy required, approximately 4–6 MJ/kg CO2.
5
Fig. 4. Number of studies vs. year.
efficiency if a high capture rate of over 92% was required [95]. capture and reduce the size of equipment (causing lower capital and
The final flue gas is de-ashed and recirculated (depending on the fuel energy cost), attempts have been made to design and propose hybrid
type about 70% vol. at 310 ◦ C [96]) again to combustion chamber in combustion configuration composed of post- and oxy-fuel combustion
order to control the flame temperature [97]. Recirculation is also used to commonly called partial oxy-fuel or partial oxy-combustion [106].
compensate the lack of N2 and ensure there is sufficient gas to transfer However, this hybrid configuration is not economically feasible for new
heat from the combustion chamber [98]. Different thermal, physical, plants. Therefore, oxy-fuel combustion continues to be the efficient
and chemical properties of CO2 and N2 (shown in Table 3) resulted in a technology even if, over a short period of time, the lack of commercial
difference between oxy-fuel combustion from air-fuel combustion in experience entails a high financial risk [60]. Compassion of post-
terms of heat transfer and flame temperature, which play a key role in (20.56% vol. O2), oxy- (95.00% vol. O2), and partial oxy-fuel combus
the design, optimization, operation, and scale-up of the furnaces [43]. tion CO2 capture configuration (55.70% vol. O2) vs. base case plant
Although, conveying velocity in oxy-fuel combustion is reduced due to without CO2 capture unit (20.56% vol. O2) using data extract from Cau
the different density and viscosity of CO2, especially the much higher et al. research [60] was shown in Fig. 6 for a 1000 MW coal chemical
density in comparison with N2 [65], the increase in the heat conduc power input. They propose partial-oxy fuel combustion due to higher
tivity coefficient causes a slight increase in convective heat transfer experience on commercial-scale in contrast to oxy-fuel combustion.
coefficient under the oxy-fuel combustion, compared with air-fuel However, there are some other design challenges including the
combustion [99]. However, with decreasing velocity, NOX formation semi-closed nature of the power cycle and the need for the integration of
may increase due to the increased residence time in the hot temperature this cycle with ASU [95]. Another challenge is designing the cycle with a
zone [100]. However, the heat transfer process during oxy-fuel com pressure ratio that is usually much higher than that of the conventional
bustion should be similar to that of air-fuel combustion in order to assure natural gas-fired combined cycle (NGCC) leads to additional challenges
the compatible operation of air and oxy-fuel combustion in a new boiler, in the design of the aerodynamic compressor [107].
or retrofit an existing boiler [99]. Experimental investigation a 3 MW In addition, the partial-oxy fuel combustion method will increase the
pilot-scale oxy-PCF furnace indicated 26–30% vol. O2 purity, has a CO2 concentration, although the increase is not enough to use the
similar heat transfer process with air-fuel combustion [71]. Finally, CO2CPU process. Therefore, the use of chemical absorption methods
theoretical and experimental studies show that the current oxy-fossil such as amine scrubbing process for effective absorption of CO2 is
fuel boiler can be retrofitted with little changes in boiler pressure inevitable. This study also used the same method using monoethanol
structure [101] and/or turbulator position of the burner [102]. amine (MEA) as solvent. The fact that any rise in CO2 concentration will
The utilization of high purity oxygen rather than air in oxy-fuel increase the corrosion rate of the equipment even more than what
burning reduces fuel consumption and consequently mass and volume happens in post-combustion method has not been considered in Cau
of the flue gas, decrease heat lost in the flue gas, and reduces the capital et al. research.
cost through decreasing the size of stack and the flue gas treatment The fact that CO2 must be ultimately delivered at high pressure for
equipment (about 75%) [102]. Projected costs have generally been utilization, storage and/or enhanced oil recovery (EOR) has led to an
comparable with those for current pre- and post-combustion capture interest in pressurizing the oxy-combustion process. This method has
techniques. The cost of oxygen production and that of compression and been developed as an advanced oxy-combustion technology. In addition,
purification of the CO2 product are the main costs compared with the near-zero level of SOX and NOX emission and higher plant efficiency as a
conventional post-combustion method [103]. However, over the last result of the latent heat recovery can be achieved using pressurized oxy-
decade, oxy-fuel combustion has attracted more attention in industrial combustion systems [13]. According to the previous studies, the plant
applications because of improving the air separation process and efficiency can be increased by around 3% if the operating pressure of the
reducing the operational cost as a critical factor affecting CO2 capture. boiler increases to around 10 bar and the latent heat of the moisture is
Furthermore, the oxy-fuel combustion technology is preferred for recovered in the flue gas [108]. Furthermore, high pressure decreases
commercialization since it is more advantageous than other processes in the gas volume and consequently reduces the equipment size and capital
terms of assembling, operating, and retrofitting [104]. Based on the costs. Theoretical and pilot-scale experimental studies indicate that over
above-mentioned oxy-fuel combustion advantages, this approach 90% of the co-removal of SOX and NOX can be achieved in a single
promises to become more and more interesting for future applications column, with water as the working fluid at a residence time of 120 s
[105]. To enhance the performance of post-combustion method of CO2 [109]. Pressurized oxy-fuel combustion of coal is a promising
6
Fig. 5. Thermos-physical properties of flue gas in different conditions, a) in burner zone that radiation heat transfer dominant b) in furnace exit that convection heat
transfer is dominant.
transported via a pipeline (dense phase) or by ships, rail, and trucks

Table 3
(liquid phase). Pipelines are the most economic, reliable, and efficient
Thermo-physical properties of CO2, N2, and H2O at 0.1 MPa, and 1000 K [76].
means of transporting large amount of CO2 which ensures that CO2,
Physical property CO2 N2 H2O captured from primary sources like fossil fuel power plants, is continu
Density, ρ (kg m-3) 0.529 0.337 0.217 ously transported to the storage site [111].
Specific heat capacity, CP (J kg-1 K-1) 54.32 32.71 41.29 As a non-toxic, non-flammable, and naturally abundant material,
Dynamic viscosity, µ (Pa s) 4.13 × 10-5 4.16 × 10-5 3.76 × 10-5 CO2 can be used in different applications such as working fluid in power
Thermal conductivity, k (W m-1 K-1) 0.071 0.066 0.097
Thermal diffusivity, α (m2 s-1) 1.08 × 10-4 1.68 × 10-4 1.95 × 10-4
cycle [112], urea production [113], EOR process [114], and etc.
Although very high purity CO2 is achievable from a technological
perspective, high concentration CO2 is not required for the CCS object
technology for carbon capture, utilization and sequestration, on which and high purity associated increasing operation cost in capture point.
more research is expected to be done in future. Furthermore, high purity CO2 stream required higher strength/specifi
cation transport pipelines to reduce the risk of ductile fracture [115].
4. CO2 quality requirements However, the delivered CO2 usually contains impurities at certain levels
depending on the fuel type, combustion technology, and several other
Flue gas specifications from two oxy-fuel combustion power plants, i. factors. The impurity can significantly affect the safe and economic
e. NGF-fired (467 MW) and PCF-fired (596 MW) are presented in transportation as well as CO2 stream phase behaviors’ [116]. It also may
Table 4 [110]. cause the chain some problems such as erosion [116], corrosion [117],
The separated CO2 should be compressed, transported, and stored to free water and hydrate formation [118], increased compression work
establish the whole chain of CCS. Based on its phase, CO2 can be [119], as well as safety, toxicity, and environmental problems [120].
7
Fig. 6. Compassion of post-, partial-oxy, and oxy-fuel combustion CO2 capture configurations vs. base case without CO2 capture unit.
- Pressure losses is negative effect and increase costs and pipelines are
Table 4
designed to avoid high pressure losses. However, increase in pressure
Oxy-fuel combustion power plant, flue gas specifications.
(for example in downhill) may affect pipeline joints/seals, erosion,
Stream NGF PCF leakages, or necessitate the installation of pressure reducing stations
Mass flow (kg/s) 61.1 180.2 [116].
P (atm) 1.5 1.5 - Only SO2 impurities resulted to lower pressure losses than pure CO2
T (◦ C) 120.0 120.0
in horizontal pipelines.
CO2 75.1% 62.6%
H2O 15.0 16.9% - Heat loss is a positive effect because lead to a denser fluid and
Ar 4.8% 1.9% decrease pressure losses.
N2 3.2% 13.5% - Lower critical pressures (PC) decrease compression duty and
O2 1.9% 4.9% following cost. All impurities increased PC above that of pure CO2.
SO2 163 ppm 896 ppm
- Lighter gases reduce the density while heavier gases increase the
NO 125 ppm 578 ppm
NO2 1 ppm 1 ppm density.
Since reduced impurity of CO2 product stream decreases operational

Furthermore, the impurity may influence the design, operation, and cost, CO2 purity above 95 vol% is recommended in a final product.
optimization through affecting the thermodynamic properties of the CO2 Table 5 shows the different post-treatment specifications of the CO2
stream [121]. Therefore, CO2 stream impurity must be reduced to stream based on various applications and industries. However, there are
decrease the aforementioned operational and environmental problems not precise standards for CO2 specification, similar to what are for oil,
and guarantee safe and feasible transportation, storage, and/or usage of gas, and hazardous liquids which can be attractive field of research in
CO2 [122]. Percentage deviation of thermodynamic properties due to future.
impurities using data extract from Peletiri et al. [116] was shown in To achieve effective compression and decrease compression works,
Fig. 7. non-condensable gases such as N2, Ar, H2, and O2 must be lower than
According to Fig. 7: 5 vol%. H2 has the highest impact on increasing the compression works
Fig. 7. Percentage deviation of thermodynamic properties due to impurities.
8
Table 5 These components can reach standard limits using various methods such
specifications of CO2 after treatment. as desulfurization process [132] for SOX pollutant and humid air method
Canyon Reef US pipeline Weyburn Dynamis project [133], exhaust gas recirculation [134], or low NOX burners [135] in
projecta[123] [124] EOR project [122] order to reduced NOX component. However, these emissions can be
[125] simultaneously removed with high efficiency from oxy-fuel combustion
CO2 > 95% > 95% > 96% > 95.5% flue gases using the CO2CPU process as one of the most advantageous
CnHm < 5% and the < 5% < 0.7% < 4% (Saline processes than other technologies [136]. Therefore, traditional flue gas
dew point aquifers) < 2% desulfurization and de-NOx processes can be ignored for pollutants
< − 28.9 ◦ C (EOR)
CO – – < 0.1% < 2000 ppm
control [137]. However, due to the high possibility of SOX accumulation
N2 < 4% < 4% < 300 ppm < 4% in combustion chamber in effect of flue gas recirculation, the primary
O2 < 10 ppm < 10 ppm < 50 ppm < 4% (Saline recycle should be de-SOX especially in case of sulfur intensive fossil fuels
aquifers) to decrease corrosion [138]. Exhaust NOX and SO2 emissions in raw flue
100–1000 ppm
gas (before cooling and dehydration step) for different combustion
(EOR)
H2S < 1500 ppm 10–200 ppm < 0.9% < 200 ppm systems were shown in Fig. 8 [71].
H2O < 0.481 gr/ < 0.481 gr/ < 20 ppm < 500 ppm Formation of CO from CO2 is strongly increases with increased gas
MMm3 MMm3 temperatures through thermal dissociation and dominates above
SOX < 1450 ppm – – < 100 ppm 2700 ◦ C (near burner region), which is about the adiabatic flame tem
NOX < 100 ppm
perature of pure oxy-fuel combustion of natural gas. Depending on the
– – –
Ar – – – < 4%
Temp. < 48.9 ◦ C < 50 ◦ C < 50 ◦ C – maximum temperature of the combustion chamber and N2 volume
a
fraction’s, an excess O2 was injected to decrease the CO formation [61].
The first large CO2 pipeline in the USA in 1970 (352 km and 12,000 t/day) in
However this spices has not significant effect on CO2CPU process.
order to usage for EOR project. CO2 pipeline through populated areas should
have a lower specified maximum SOX, and/or H2S content.
Finally, to moderate impurities’ effect on a two-phase flow’s feasi
bility, it is necessary to increase the CO2 transport pipeline’s operating
pressure and identify appropriate points of re-pressurization [139]. The
desirable effect of main impurities in CO2 stream are summarized in
[122], although H2 and CH4 do not exist in oxy-fuel combustion flue
Table 6.
gases. Since combustion is done with excess oxygen, a small amount of it
is always observed in the exhaust gases, which must be reduced ac
cording to the application of CO2, as shown in Table 5.
H2O, as the most undesirable kind of impurity and the corrosion rate
Table 6
of pipelines transporting dry CO2 increases from an order of µm/year to
Main desirable effect of impurities in CO2 stream.
mm/year in the presence of free water [126]. Water solubility in CO2
sharply decreases when the pressure rises to 50–60 bar and rapidly in Impurity Main desirable effect
creases when the pressure is stabilized at 60–80 bar [127]. Furthermore, O2 In EOR process causes overheating at the injection point and
when the pressure and temperature change, H2O molecules transformed oxidation and biological growth in the reservoir [110]
Accelerated the corrosion in equipment and pipeline [140]
into solid phase and trigger hydrate formation and, consequently,
H2O May lead to the formation of carbonic acid [138]
erosion and/or blockage in the pipeline [128]. Notably the risk for hy May lead to the trigger hydrate formation [128]
drate formation exist up to 10 ◦ C at current transportation pressures SOX Hazardous and toxicity substance
[129]. Therefore, the maximum allowable H2O content in the CO2 Corrosive material and accelerated the corrosion in presence
pipeline must be determined before CO2 transportation. Based on of water [140]
H2S Hazardous and toxicity substance
Table 5, H2O content is recommended to be kept under 50 ppm. Corrosive material and accelerated the corrosion in presence
In addition to the SOX and NOX’s toxicity, in case of these pollutions of water [140]
vent to atmosphere they contribute to acid rain, cause photochemical Non-condensable Increase saturation pressure [141]
smog, cause ozone depletion and thus pose a detrimental health and gases Increases the pipeline inner diameter and thus the relative cost
per km of pipeline [142]
environmental hazard [130]. Therefore, concentration limit of these
Increase compression works
components in CO2 is fixed according to health, safety, and environ Reduction in storage capacity [143]
mental regulations and the use of carbon dioxide. If chemical absorption NOX Hazardous and toxicity material
processes such as the amine scrubbing process are used, these compo Corrosive material and accelerated the corrosion in presence
nents can form heat stable salts, which are severely corrosive [131]. of water [140]
Fig. 8. Exhaust NOX and SO2 emissions in different combustion systems.
9
5. Capturing CO2 using CO2CPU process the principle of phase separation process based on cooling and
condensation. In terms of the total cost of clean power production, this
5.1. Process description unit is similar to post-combustion CO2 capture using an amine scrubbing
process [145]. Fig. 9 shows the process flowsheet of CO2CPU, an
Oxy-fuel combustion flue gases are mainly composed of CO2 and auto-refrigerated system designed based on the Joule-Thomson effect
H2O, out of which the CO2 can be captured without difficult via water [146]. To avoid pipes and tubes’ erosion resulting from the formation of
condensation. However, a CO2CPU system is still required to decrease hydrate and decrease the equipment’s corrosion, the flue gas should be
the amount of un-reacted O2 and other non-condensable gases and meet cooled and dehydrated before it is fed to this unit [147]. Hence, the
the CO2 quality requirements for transportation and storage [142]. maximum water in the feed gas must be decreased to 50 ppm before the
CO2CPU process, proposed by the International Energy Agency Green inlet to the CO2CPU process [122]. The first step is initial purifying and
house Gas (IEAGHG) R&D Programme [64], is an appropriate process dehydration of flue gas using cooling and condensation, where the water
for capturing CO2 from oxy-fuel combustion flue gases which contains a content, ash, and inert gases are removed. Thereafter, the flue gas after
high CO2 portion. Depending on their various uses, several process cooling and dehydration by direct contact column (DCC) with cooling
flowsheets have been offered for the CPU process. However, the CO2CPU water (CW) is fed to a dual bed drier to further water content reduction.
process equipped with two flash drums is selected for oxy-fuel com Although, it is important to increase the outlet temperature of the CW to
bustion applications. It is an auto-refrigerated process characterized by its maximum level in a way that the heat integration has the highest
lower capital costs and fewer power consumptions compared to CO2CPU energy, in practice, the temperature of the flue gas at the inlet of DCC is
equipped with distillation tower [144]. This process is an attractive required to be high enough to prevent acid-gas condensation before
method to produce high purity CO2 from oxy-fuel combustion utilizes DCC.
Fig. 9. Schematic figure of a pressurized oxy-combustion systems equipped with CO2CPU.
10
Due to the decrease in the compressor volumetric efficiency with a For dense phase CO2 pipelines, both operating condition and impu
significant increase in compression ratio [148], compressing is done in rity content have a significant effect on CO2 fluid properties. Further
two compressors equipped with intercoolers or a multi-stages more, temperature changes have greater effect than pressure changes
compressor (MSC). In order to minimize the content of water, each [159]. CO2 density may significantly change with a small change in the
intercooler has a condensate trap for discharging water droplets before operating conditions near CO2 critical point. For instance, a reduction of
the inlet to the next compressor stage. The compression ratio method is a about 10 ◦ C from the critical temperature will double the density [160].
simple and straightforward approach to estimate the compression ratio Hence, CO2 transported via pipeline is of the highest amount in the
in MSC [149]. Usually, the compression ratio change between 1.05 and dense phase. The critical temperature and pressure of CO2 are 31.1 ◦ C
11 per stage [150]. An increase in the gas temperature during the and 7.38 MPa respectively. The minimum pressure of a CO2 pipeline is
compression limits the pressure rise or safety [151]. The maximum about 10%, greater than the critical pressure of the flowing fluid [161].
temperature rise is controlled by either the compressor cylinder’s However, even an ordinary change in the ambient temperature (or soil
maximum operating temperature (usually below the 200 ◦ C [152]) or temperature in a buried pipeline) can lead to a two-phase mixture in the
the maximum temperature which the gas can resist before polymeriza pipeline, which is required to be prevented [162]. However, if the
tion, decomposition, even auto-ignition. pressure is greater than 9.6 MPa, it can guarantee that CO2 will be
More than 80% of flue gas in the oxy-fuel combustion process con transported in the supercritical state at any temperature [163].
sists of CO2, considered a neutral gas. Thus, a high compression ratio can Furthermore, based on risk, consideration safety, and economy the
be used if the compressor manufacturer complies with the maximum maximum pressure of CO2 pipeline can reach to 30 MPa for far away
allowable temperature. However, with an increase in the compression from populated areas [163]. Therefore, it influences the hydraulic sys
ratio, the volumetric efficiency decreases, leading to limiting discharge tem of CCS pipeline systems, both technically and in terms of cost [164].
pressure. Optimum minimum horsepower is obtained when the Finally, the CO2CPU process is designed using two and three cold-
compression ratio is the same in all cylinders for MSC. Intercoolers are boxes with/without a distillation tower. However, since the current
commonly used on the MSC to decrease the gas temperature to the process flow diagram (PFD), i.e. using one cold-box, is more desirable
original suction temperatures with a little pressure drop [153]. than the other ones, which operate in the same way, the other structures
The number of compression stages can be calculated using Eq. (1) are not explained here.
[154]:
5.2. Thermodynamic equation of state
P2/P1=kn (1)
where k represents the compression ratio, and n indicates the number of The content of flue gas depends on the fuel used and the power
stages. Up to 5 stages of compression were applied in some studies, plant’s performance [165]. The existence of impurities such as N2, H2O,
increasing the investment cost. When a high compression ratio is Ar, O2, SOX, and NOX, can change the thermodynamic, phase behavior,
needed, or the outlet stream is too hot, the number of stages inevitably chemical effects, and transport properties of the CO2 stream of oxy-fuel
increases [155]. Following cooling and dehydration, the raw flue gas is combustion and then affect the process design optimization, and oper
compressed up to 30 bar. To cool the stream S5, then the pretreated flue ation. Equation of state (EOS) modeling is an appropriate approach
gas is sent to the cold-box. After cooling (termed S6), this stream turns which has been widely applied to investigate the fluids phase behavior.
into a two-phase fluid and then, enters into the first flash drum (F1). Furthermore, based on simulation results, pressure-volume-temperature
With due regards to the difference in the boiling point components, (PVT) properties have significant effects on the ultimate recovery and
some CO2 condensate in F1 is eliminated from the circuit with a purity of the predicted production profile [166]. Therefore selection of appro
96% or higher (stream S14) then recirculated to the cold-box as refrig priate thermodynamic EOS is a vital stage in theoretical and simulation
erant after passing through a throttle valve (TCV1). Two throttle valves researches which are done based on the nature of mixture, operating
(TCV1 and TCV2) are utilized for occurring the Joul-Thomson effect. conditions, and data availability [167].
The CO2CPU process is known as an auto-refrigeration unit. Instead of Due to the use of high purity O2 in oxy-fuel combustion, the exhaust
supplying external utilities to the unit, product streams obtained from gas mostly consists of CO2, H2O, and a small amount of inert gases and
flash drums are recirculated to the system as coolants. The process is un-reacted O2 [168]. However, the CO2 and H2O vapor have the major
conducted in two flash drums with different temperatures (− 35 ◦ C and contribution to radiation heat transfer due to have high emission and
− 55 ◦ C, respectively) to decrease energy costs. It must be noted that absorption coefficients than N2 [169]. Therefore these species promotes
process operating temperature shall always be above the triple point radiative heat transfer compared to air-fuel combustion.
temperature of CO2 (i.e., − 56.57 ◦ C) to avoid CO2 blocking and/or so In theory, NOx are not produced in oxy-combustion since the
lidification [156]. To be condensed and more cooled, the gaseous part oxidizer does not include N2. However, in practical due to presence of N2
from the top of the first flash separator (S7) is returned into the cold-box. in the O2 feeding stream from cryogenic ASU, the combustion of low
Consequently, it changes again to a two-phase mixture and then sent grade fuel containing N2, and air-leakage into industrial combustion
to the second flash separator (F2) for the separation of the rest of CO2. chambers from ambient air generates NOx [170]. NOx emissions mainly
The high-pressure stream from the top of the F2 (S9) is fed back to the consist of nitric oxide (NO), and to a lesser degree nitrogen dioxide
cold-box as the cooling agent and then leaves the cold-box at 75 ◦ C (NO2), as well as nitrous oxide (N2O). However, based on experimental
(S10). The vent gas can be more expanded in a turbo-expander to investigations, oxy-fuel combustion will result in lower NOX and SOX
generate shaft power or electric power. Therefore, a gas turbine is uti emissions compared with air-fuel combustion [171]. The NOX emission
lized to generate power before it vents at atmospheric pressure. Due to decreases due to the absence of N2 in the furnace’s feed gas and its
the turbines’ expensiveness and to reduce fluctuations in the stream fed decomposition when it, along with flue gas, is recycled to combustion
to the turbine, the stream is heated to 100 ◦ C [157]. Increasing in inlet [172], as well as, the high CO2 and CO content suppresses NOX forma
gas temperature will also rise the amount of generated power [158]. The tion [65]. In case of oxy-PCF combustion, NOX formation is also function
stream leaves the turbine (S12) at 2.2 bar and − 37 ◦ C and is fed back to of motion pattern, shape, and size of fuel particles in combustion
the cold-box as a coolant and then vent to the atmosphere at 28 ◦ C (S13). chamber [65].
At last, all CO2 products from the bottom of the two separators are mixed However, after direct water cooling and dehydration, most of these
and compressed to be permanently stored or utilized through pipelines impurities and dust are removed, and the significant components of the
in the form of gas phase, supercritical (dense) phase or subcooled liquid stream will include CO2, N2, and O2. Therefore, the oxy-fuel combustion
state. flue gases can be regarded as a mildly nonpolar mixture. As a result,
Peng-Robinson (PR) [173] and Soave-Redlich-Kwong (SRK) [174]
11
thermodynamic EOS were recommended by AspenTech for these mildly heat source and the working fluid [180]. Various cycle configurations
nonpolar mixtures [175]. However, the PR was selected as the most using oxy-fuel combustion, such as NET Power cycle [181], Graz cycle
appropriate EOS to estimate the thermo-physical specification of CO2 [182], semi-closed oxy-fuel combustion combined cycles (SCOC-CC)
stream containing a spot of impurities and the range of temperatures [183], clean energy systems (CES) cycle [184], and Allam cycle [185],
(− 60 to 250 ◦ C) and pressures (1–120 bar) [38]. The PR EOS can be have been proposed and developed over the recent years. The type of
written as [173]: dilution substance which recirculated to combustion chamber may
change the cycle configuration of oxy-fuel combustion systems. For
RT a
P= − (2) example, in SCOC-CC as the closest to the conventional NGCC in regard
V − b V(V + b) + b(V − b)
to the system configuration [95], the water vapor is separated by
where: condensation and only CO23 is recycled to the combustion chamber
[183] or a mixture of CO2 and water vapor is used for dilution in the
[ ( √̅̅̅̅̅ ) ]2
T Graz cycle [182].
a=λ 1+β 1− (3)
Tc
5.3. Economical evaluation
R2 T2c
λ = 0.45723553 (4)
Pc
5.3.1. compressor
Eq. (9) calculates the investment costs of compressor and or multi-
β = 0.37464 + 1.54226ω − 0.26992ω 2
(5)
stage compressor (Ccomp) where ṁ is the mass flow rate (kg/s), Pin and
RTc Pout are the inlet and outlet pressure (bar), respectively [186].
b = 0.077796074 (6) [ ( )]
Pc ( ) ( ) Pout
Ccomp = ṁ 0.13 × 106 ṁ− 0.71 + 1.4 × 106 ṁ− 0.60 ln (9)
Pin
where P and T are the pressure and absolute temperature, respectively; R
is the universal gas constant, V is the specific molar volume, TC and PC
5.3.2. Cold-box
are the critical temperature and pressure, respectively; a and b are the
Since most cold-box streams’ were in gas state, the overall heat-
dimensionless constants describing attractive and repulsive forces,
transfer coefficient is assumed to be U= 170 W/m2K [187]. The
respectively; ω is Pitzer acentric factor,2 and λ is a dimensionless func
cold-box heat-transfer area (A) can be obtained using Eq. (10):
tion of TC, PC, and R. For a mixtures system, the following classical van
der Waals mixing rules are used to calculate the parameters a and b in Duty
A= (10)
Eq. (2): U. LMTD
∑N ∑N √̅̅̅̅̅̅̅̅ Total volume of cold-box can be obtained using a conservative esti
a= xi xj ai aj (1 − kij ) (7)
i=1 j=1 mate of 78 m2/m3 for a plate heat exchanger [188]. Brazed aluminium
∑N plate-fin heat exchangers are very compact heat exchangers built to a
b= i=1
xi bi (8) high specification for use in different application such as petrochemical
industry and refrigeration system and is assumed to be used as the
where x represents the molar fraction in the liquid or the vapor phase, cold-box. All aluminium alloys have advantageous behavior at low
and kij denotes the temperature-dependent binary parameters between temperatures (to − 269 ◦ C). Therefore, only the maximum design tem
components i and j, assuming the value zero for i = j. This parameter can peratures are of importance for aluminium alloys [189]. The cost per
be obtained from the regression of phase equilibrium data. The experi unit volume Cvol. (104 US$/m3) for the aluminium plate-fin heat ex
mental kij for PR and SRK EOSs are summarized in Table 7. These changers with 4–6 streams be estimate using Eq. (11). The maximum
interaction coefficients are accounted for the attraction forces between volume of a cold-box using this equation is limited to 11 m3 and split
pairs of non-similar molecules [176]. Although these interaction co into parallel trains with the same volume when the total volume exceeds
efficients for PR EOS have an insignificant effect on specific compression 11 m3.4
power and cooling duty, they play an essential role in calculating CO2
purity and separation efficiency. Cvol. = − 0.009541v3 + 0.253v2 − 2.298v + 9.412 (11)
The critical temperature and pressure of CO2 are 31.1 ◦ C and The installed cost of cold-box, CCB (US$), can be calculated based on
7.38 MPa respectively which can easily reach to its supercritical state. It Eq. (12) [186].
is advantage in case of using CO2 as working fluid for low temperature
power generation [179], due to decrease in thermodynamic losses CCB = fm Nrp Cvol. VCB (12)
resulting from irreversibilities during heat transfer process between the
where fm is the total module factor that converts the purchase cost into
the total installed cost (for cold-box fm=2 [190]), N is the number of
Table 7
parallel trains, rp is cost ratio for operating pressures; rp = 1 for pres
The experimental kij mixing parameters for PR and SRK EOSs.
sures below 25 bar and rp = 1.1 for pressures between 25 and 40 bar,
Comp. i Comp. j kij for PR Refs. kij for SRK Refs. and VCB (m3) is the volume of a single-train cold-box [186].
CO2 Ar 0.1230 [177] − 0.076 [176]
CO2 O2 0.1116 [177] 0.168 [176] 5.3.3. Separator
CO2 N2 − 0.0115 [177] 0.102 [176]
For determining the size of separators, the maximum velocity of the
CO2 SO2 0.0559 [177] − 0.041 [176]
CO2 H2S 0.0990 [176,178] 0.083 [176]
CO2 CH4 0.1000 [176,178] 0.079 [176]
O2 N2 − 0.0119 [177] 3
– – CO2 has a stronger chemical effect than H2O on laminar burning velocity.
4
This equation obtain using curve fitting based on data from ESDU in 1997
(Selection and Costing of Heat Exchangers, Plate-fin Type). An exchange rate of
1.6 from Great British pound to United States dollar in the year 1997 has been
used. The goodness of fit this equation: SSE= 0.007035, R2 = 0.9997, and
Adjusted-R2 = 0.9992. The final cost must be update using cost index. This
2
This factor used to characterize the shape of a molecule. method presented at end of this section.
12
vapor stream was used based on Eq. (13) [191]. In this equation, FFactor is plant with a gross power output of 357 MW. They found that, via heat
equal to 1.0 in English Engineering measurement system and 0.6 in SI integration between various subsystems, such as CPU and ASU, with the
system [191]. turbine, the net efficiency penalty could decrease from 12.7% to 8.5%.
√̅̅̅̅̅ Ritter et al. [202] presented, through energetic performance evalu
Ffactor = Vmax ρv (13)
ation, six conceptual CO2CPU schemes to improve thermodynamic ef
ficiency and reduce their specific energy consumption. Pipitone and
where Vmax is the maximum vapor velocity in m/s and ρv is the vapor
Bolland [110] simulated two different process flowsheets of CO2CPU
density in kg/m3.
process for two different oxy-fuel flue gases coming from NGF and PCF
√̅̅̅̅̅̅̅̅̅̅̅̅
Q plants, based on phase separation using SRK-SimSci EOS in SIMSCI
D=2 (14)
πVmax PRO/II® environment. The first configuration was equipped with two
separators working at − 26 ◦ C and − 54 ◦ C and the second one had a
In Eq. (14), D is the diameter of the separator and Q is the vapor
distillation tower with ten stages. In the second scheme, the propane
volumetric flowrate in m3/s. The aspect ratio L/D was considered 2
loop between 20 atm and 3.7 atm was used to reach − 54 ◦ C in the
[191]. Assuming a hemispherical head is used, the volume of drums
partial condenser in the distillation column. High purity CO2 product
VDrum (m3) can also be calculated by:
(99.3%) was removed from the bottom of the distillation column in the
π D2 liquid phase at T = − 10 ◦ C and P = 29 atm, and its pressure was
VDrum = (2D + 3H) (15)
12 increased to 110 bar with a pump. Using the first configuration, CO2
recovery factor, it was found that 96.2% and 88.1% with NGF and PCF
The volume of vertical flash separators can also be estimate by [192]:
fired exhaust flue gas, respectively; while CO2 purity was over 96% in
VDrum = 2th Ḟ (16) both flue gases. In the second configuration, this factor decreased by
about 0.8% and 1.8% for NGF-fired and PCF-fired flue gases, respec
where th [s] is the half full holdup time (about 5 min [193]), and Ḟ tively. Besides, compression power consumption in NGF-fired flue gases
(m3/s) is the volumetric liquid flow. The capital cost of flash drum also operation is less than the power consumed in the operation of PCF-fired
can be obtain from following equation [194]: flue gases because it contains less impurity. However, reliability of the
SRK-SimSci EOS needs to be verified experimentally or compared with
CDrum = 17640D1.066 L0.802 (17) well-known PR EOS because the choice of the EOS has a significant ef
Vessel wall thickness can be calculated using Eq. (18) [195]. In this fect on the result and behavior of the process. Therefore, in a similar
equation D is diameter (mm), τ is wall thickness (mm), P is design study, Posch and Haider [119] simulated these process flowsheets using
pressure (barg) refer to Table 8, E is joint efficiency, S is maximum PR EOS in the Aspen Plus® environment to investigate the effect of the
allowable stress (bar) and C is corrosion allowance (mm). main design factor on these schemes’ performance. In the second
configuration, they employed a six-equilibrium-stage distillation col
PD
τ= +C (18) umn. In the next step, the performance of these configurations under
2SE − 1.2P different operating pressures was compared. Based on the results, any
Finally equipment value can be up to date through cost index data change in flue gas composition in both structures increased specific
such as Marshall and Swif equipment indexes, using following equation compression power and cooling duty through decreasing CO2 content in
[192]: the flue gas stream. Furthermore, CO2CPU configuration with distilla
( ) tion column achieved higher purity at about the same separation effi
index value at present time
present cost=original cost ciency, but with a 30% rise in power and cooling duty than the
index value at time original cost was obtained
separation by a double flash drum. Although the second scheme could
deliver CO2 in a higher concentration, the first CO2CPU process scheme
6. Summary of main results obtained from CO2CPU sensitivity showed a good performance in the presence of flue gases of low impu
analysis and optimization rity. That is why more research has been directed towards the CO2CPU
process equipped with two flash separators. Fu and Gundersen [203]
The CO2CPU as refrigeration cycle requires high energy for simulated and compared three process flowsheets of CO2CPU based on
compression, which increases the capital and operating cost due to the phase separation using flash separators for oxy-fuel combustion power
compression trains and the shaft work required to drive them, respec plants, i.e., one-stage, two-stage flash, and three-stage flash. The com
tively [197]. Minimizing the operating costs can lead to improved pro parison was performed using pinch analysis in order to increase ther
cess economics, higher energy efficiency and reduced carbon emissions modynamic efficiency and decrease energy penalty. Aspen Plus®
to the environment [198]. Therefore, sensitivity analysis and optimi (2006.5) and SimSci PRO/II® software tools were used for simulation
zation of this unit are one of the fields that have attracted many re and exergy analysis of these flowsheets. Using composite curve, it was
searchers’ attention, mostly intending to reduce the energy of CPU and found that the addition of one more stage of flash separation could
increase CO2 purity and CO2 recovery. Simulation and optimization of improve the plant performance because the exergy losses reduced more
complex processes via software simulators such as Aspen Plus®, Aspen in the sub-ambient temperatures cold-boxes. However, it was not
Hysys®, ChemCAD®, SimSci PRO/II®, gPROMS®, etc. is an appropriate regarded to be appropriate if the investment cost was also considered.
approach for saving time and cost spent on identifying the Further, investigation on these process flowsheets was conducted
thermos-physical properties and optimal operating conditions [199]. through techno-economic analysis [186]. Besides, the maximum CO2
Kakaras et al. [200,201] simulated a greenfield oxy-lignite power recovery rates for the three flowsheets at the given purity (96.3%) were
found to be 92.9%, 94.6%, and 95.0%, respectively. Finally, based on
techno-economic analysis, the CO2CPU process flowsheet with two flash
Table 8 separators was the most cost-effective structure.
Estimation design pressure vs. operating pressure [196].
Kolster et al. [38] simulated four PFD of the CO2CPU process include:
Operating pressure Design pressure (barg) 6-stage compression and dehydration process without additional puri
0–10 barg MOP + 1 bar fication, CO2CPU equipped double flash separator and with/without
10–50 barg MOP + 10% two cold-box, and finally CPU process equipped a 6-stage distillation
50–100 barg MOP + 5 barg column with one cold-box and one flash drum. Simulation were done
> 100 barg MOP + 5%
using PR EOS in Aspen Hysys® environment. They indicated that as the
13
Table 9
Comparison of the three CO2CPU process flowsheets.
Luyben [188] Jin et al. [205] Koohestanian et al. [157]
Cold Box 1 Duty (MW) 5.108 27.525 56.858

LMTD (K) 11.04 4.94 17.00
A (m2) 2721 32,786 19,674
Cold Box 2 Duty (MW) 25.910 22.007 –
LMTD (K) 4.71 4.1 –
A(m2) 32,320 31,750 –
Cold Box 3 Duty (MW) 21.400 – –
LMTD (K) 5.71 – –
A(m2) 22,000 – –
Total area (m2) 57,041 64,536 19,674
Purity % 95.17 96.65 96.74
Recovery % 90.29 90.82 90.08
MOP (bar) 30 30 29
PFD increase in complexity, product purity and energy penalty also in product stream, reduce heat utilities, and compressors’ work. The
crease, while separation efficiency decrease. Also they reported that interaction of these optimization parameters was also studied using
since several CO2 streams with different purities and different source RSM. As the statistical analysis results showed, the reduced temperature
combine into one final trunk line, so final CO2 purity in trunk line is of the first flash drum significantly affects the separation process and
important. However, the advantage of the CO2CPU process is that it is decreases the compressors’ work and heat utilities of this unit.
auto-refrigerated, and it is clear that the use of system without cold-box Furthermore, the reduction of optimal MSC outlet pressure from 30 bar
in their research is rejected in terms of operating costs. Furthermore, it to 25.34 bar decreased operating and capital costs. However, cold-
would be better that the comparison is done in a certain purity or re boxes’ heat transfer area was not considered in that study as crucial
covery. In addition, no attempt was made to improve the process equipment in cost analysis. In another research, they focused on modi
flowsheet or optimize the operating conditions of the process. While, fying the CPU process flowsheet to improve the process’s structure and
comparing optimized processes and/or improved structure may indi performance and its realistic view of controllability [157]. Also, the
cated different results. It is also not necessary to choose very high CO2 number of cold-boxes decreased to one device, and the feasibility of the
purity. Furthermore, depending on the usage of CO2, these impurities process flow diagram was investigated through dynamic response in the
can even be useful. For example, if CO2 is used in the urea production, it face of disturbances. Comparison of the three CO2CPU process flow
is generally necessary to add some oxygen as an oxidizing agent to sheets based on phase separation using two flash separators for identical
reduce the corrosion in the stainless steel equipment in the urea plant flue gases are summarized in Table 9.
[204]. Through experimental research on a sample oxy-fuel flue gas with a
However, the distillation process was introduced with the highest 50 kg/h flowrate, Hai-Bo et al. [207] verified the CPU process’s feasi
purity of the output product and the highest cost, which is consistent bility. They demonstrated that this unit could capture CO2 with high
with the previous results [110]. purity. They revealed an increase in the operating pressure from
Using single variable analysis, Jin et al. [205] investigated the effect 2.5 MPa to 3.4 MPa significantly decreased the energy consumption.
of operating parameters on system performance for the CO2CPU process Also, the optimal operating conditions for liquefaction were reported to
equipped with double-flash separators using PR EOS in Aspen Plus® be − 30 ◦ C and 3.0 MPa. Although details such as PFD and mass and
(version 7.1). They also conducted multi-variable optimization to find energy balance were not presented in this research, it is inferred that the
optimal and robust operating conditions and control system design using process structure used by them differs from the structure of the
Aspen Plus Dynamic® (version 7.1). The objective function includes auto-refrigerated CPU process, leading to different results. They used a
maximizing CO2 recovery from raw flue gas while minimizing the spe scrubbing tower to separate SOX and NOX. In the CPU process, these
cific power consumption. Based on the single variable analysis results, components were well separated by the separators, and the use of
increasing MSC discharge pressure from 28 bar to 33 bar improves re scrubbing tower in addition to increasing the capital cost is not so
covery rate by 1.11% while decreasing CO2 purity of the product by common.
0.71%. The reported optimal operating conditions were 30 bar, Xu et al. [208] proposed new process flowsheet for oxy-fuel com
30.42 ◦ C, − 24.64 ◦ C, and − 55 ◦ C for MSC discharge pressure and bustion flue gas treatment. They state the concentration of SOX in the
temperature, and the first and the second flash drums’ temperature, oxy-fuel combustion are much higher in compared with that in air
respectively. These conditions decrease specific power consumption up combustion, which decrease the performance of the selective catalytic
to about 2.58% and increase the CO2 recovery rate by about 0.09%. reduction for NOX removal. Regarded to SO2 and NO2 dew points are
Dynamic results of this work are summarized in the next section. much higher than that of CO2, they suggests that partial CO2 liquid can
Using these optimal conditions and thermo-economic cost analysis of be recycled to liquefy these impurities in the CO2 stream in the absence
the CO2CPU process, Jin et al. [144] illustrated that although the unit of water. Finally, the SOX and NOX removal units were designed for the
thermo-economic cost for MSC is the least value among all equipment, treatment of streams rich these pollutants. Simulation, and sensitivity
the investment cost of compressors is about 92.33% of total cost in analysis of operating conditions on the performance of CO2 recovery,
vestment (57.35 M$). These results were consistent with the previous CO2 purity, and NOX and SOX content were done through Aspen Plus®
research [186]. software. Result of simulation design validate using experimental data
Koohestanian et al. [206] investigated sensitivity analysis and obtained from a simplified pilot-scale testing platform. Based on their
multi-objective optimization of the CO2CPU process equipped with two results a CO2 stream with a purity of 99.9% could be achieved, and the
flash separators by designing an experimental approach based on distillate after treatment in SO2 and NO absorbers could be directly
response surface methodology (RSM). The temperature of flue gas recycled back to the boiler.
before, during, and after MSC compression, two flash drum inlet tem However, there is no serious concern about content of this pollutant
perature, and MSC outlet pressure were chosen with three levels as the in raw flue gas. Furthermore, theoretical investigation indicated in
effective optimization parameters to increase CO2 flowrate in the cooling and condensation stage using DCC (refer to Fig. 9) 99.9% and
14
70% of SO2 and NOX are removed, respectively [209]. identify the best control strategy. Then, uncertain RGA analysis was
Finally, the CO2CPU process alone is able to remove a significant done to examine process nonlinearities. While preventing CO2 freezing
portion of these pollutants, and these pollutants are within acceptable within the system, the proposed control structure could keep CO2
content in the final product [205]. Furthermore, the use of distillation product purity and CO2 recovery at the initial set-point value, i.e., 95%
towers to remove CO2 from oxy-fuel flue gas has been previously and 89%, respectively, in the presence of process disturbances.
rejected for economic reasons [38]. They also suggest that the vent Having optimized the CO2CPU process with two flash separators in
stream can inlet to the combustion chamber as a recycle flow, in which the Aspen Plus® (version 7.1) using multi-variable optimization, Jin
case, according to data reported for vent stream, it causes the accumu et al. [205] modeled this process in Aspen Plus Dynamic® environment.
lation of argon and nitrogen in the cycle, which can be problematic if the A pressure-driven approach was used for rigors modeling. A single and
system is examined dynamically in the long term. Therefore, it is double temperature control strategy was then designed to obtain a
necessary to discharge the vent flow into the atmosphere, which reduces robust control structure and maintain operating targets around optimum
CO2 recovery. Also, the content of SOX in the flue gas is more a function conditions. Three constraints were chosen based on product quality re
of the type of fuel than the combustion method (refer to Table 4 and quirements in order to reach profitable operations and products. They
Fig. 8). included CO2 product purity of 96% or above, avoiding CO2 solidifica
tion through keeping the temperature above the CO2 triple point (i.e.,
7. Dynamic investigation and control − 56.67 ◦ C) and maintaining CO2 recovery rate at its initial set-point
(above 90%). Finally, it was found that a single temperature control
CPU shall be able to bear on the abnormal situation and disturbance structure was not an appropriate approach for controlling the CPU
in upstream. Feed flowrate, feed temperature, and feed composition are process. However, apart from being too complicated, this control
the essential disturbing parameters that influence the performance of structure would not be robust for a long time as it leads to running dry or
the CO2CPU process. Commercialization is needed to increase the overfilling of the flash drum [188].
technology readiness levels of any new process by developing a pilot Luyben [188], presented a simple control structure for the CO2CPU
plant followed by a bench setup, which is an expensive proposition. process equipped with two flash drums and increased the degree of
Dynamic modeling and simulation helps study transient responses, freedom by increasing the number of cold-boxes to three. As recovery
identify and eliminate the gaps, save cost and time of investigation of the and purity insignificantly changed against severe disturbances, they
process performance, develop and/or adjust control system in the face of were not needed to be explicitly controlled, especially due to the use of
disturbances, and improve the process’s operability and feasibility temperature and level control loops. Therefore, conventional
[210]. Furthermore, it provides engineers the opportunity to test proportional-integral (PI) controllers were sufficient without composi
different operating schemes or control strategies, workers to operate the tion measurement to cause the process to have a desirable performance.
process virtually, and operators to examine “what if” scenarios [211]. Although more superficial control structures have always been attrac
Most of the studies were done using modeling in Aspen Plus Dynamic® tive from a practical view, the heat transfer area in this scheme signif
and/or MATLAB/Simulink environment. In this section, the study re icantly increases, leading to an increase in the investment cost.
sults on the dynamic behavior of the CPU process are summarized. However, he disregarded the first separator’s thermal stabilization,
Dynamic modeling and analysis of the CO2CPU process [212] are which may lead to the saturation of control valves in the long term.
conducted in the UniSim® environment to investigate the dynamic Based on API RP 521 [217], in a series of columns where one column’s
response and improve its control structure. The robustness test was done output is fed to the next one, the thermal load of individual columns is
by applying disturbances and studying their effects on equipment required to be regulated since the decrease in the temperature a column
response. Product purity specifications are reported to be preserved may disturb the performance of the next one. Non-regulation of the first
throughout the transition while the specific energy consumption separator’s temperature will result in an insignificant but constant
increases. decrease in liquid level within the first separator, which will raise the
A dynamic model of an 800 MW oxy-coal power plant is developed liquid level in the second separator. Given that these conditions have to
by integrating a unique modeling package in Doosan Power System to be modified to prevent heating up or freezing, the control valves will be
simulate the boiler and the Aspen Hysys® to model the CPU and ASU saturated in the long run, leading to compromised process control.
[213]. To integrate these models, the boundary assumptions, including Liu et al. [218] applied two self-optimizing control structures to
the specification of variables passing between subsystems and depen minimize energy consumption (structure 1) and economic cost (struc
dent or independent systems, must be adequately determined in each ture 2) of the CO2CPU process equipped with two flash separators. They
calculation step throughout the process. implemented the same constraints previously used in Jin et al. [205]
Transient response of CO2CPU equipped with two flash separators in against five scenarios, including base case, flue gas CO2 content ( ± 5%),
response to process disturbances for an oxy-coal power plant was and flue gas flowrate ( ± 5%) as the operating disturbances. Finally,
analyzed using Aspen Plus® (version 2006.5). Relative gain array (RGA) they revealed the desirability of the first control structure in realizing
analysis was implemented to identify the most proper control structure energy- and cost-effective operation since the lowest energy-cost per
for maintaining CO2 purity at a desirable level [214]. Chansomwong formance is observed in the case of using the first control structure
et al. [215], in another work, investigated the dynamic behavior of this compared with the second one and control scheme proposed by Jin et al.
process through dynamic mathematical modeling using PR EOS in [205].
gPROMS® environment to identify dynamic behavior and proposed Koohestanian et al. [157] proposed a new process flowsheet for the
decentralized control structure based on feedback controller. The RGA CO2CPU process equipped with two flash drums and investigated dy
analysis was performed to design the control structure. CO2 recovery namic behavior and simple control structure. They decreased the num
was found to be more sensitive to the process operating condition than ber of cold-boxes to one device, which reduced the capital costs and
CO2 product purity, while it was reversed in response to changes in the improved heat integration. Compared with previous research in similar
flue gas composition. However, CO2 purity did not show any significant conditions, it was found that the new one not only can operate at lower
change over 1%. As for transient behavior, the system showed a operating pressure (29 bar instead 30 bar) but also cause a reduction in
nonlinear behavior. The temperature of the stream fed to the first flash cold-boxes’ heat-transfer area. The control structure was designed based
separator was the most important parameter affecting CO2CPU perfor on conventional proportional (P) and PI controllers. Regarding dynamic
mance measured by the CO2 recovery and CO2 product purity. Accord behavior, the first separator’s temperature is required to be accurately
ingly, in another work [216], a decentralized multi-loop control and narrowly controlled to maintain process stability and prevent
structure was suggested for this process based on RGA analysis to controller saturation. Results showed that the process flowsheet was
15
robust, and purity and recovery rates in the face of disturbances were the process become operational. Hence, some improvements and
maintained at 96.74% and 90.08%, respectively. However, due to this potential control strategies are necessary to approach dynamic
system’s severe nonlinearity, controllers are suggested to be returned if model to real plant, while attempting for optimization of the devel
the flowrate changes highly enough and permanently. oped control system.
- There is a lack of comprehensive research on calculation of details
8. Conclusions and recommendations for future research design and detail economic investigation of the CO2CPU system.
- Due to the high temperature of flue gases as well as existence CO2
Capturing CO2 from oxy-fuel combustion flue gases using the and H2O vapor as main combustion products which have much
CO2CPU process has attracted many researchers in recent decades. Oxy- higher emission and absorption coefficients than N2 an accurate
fuel combustion can be applied to both NGF and PCF as the main global radiative model is vital to estimate the heat transfer in the oxy-fuel
primary energy sources for power generation. Another feature that combustion technology. Lack of accurate radiative heat transfer
makes the oxy-fuel combustion valuable is its flexibility to integrate with model may result in a major mistake in the prediction of the
the largest primary sources of CO2 emission such as power plants or maximum and average temperature distributions inside the com
cement industry. From technical point of view, capturing CO2 from oxy- bustion chamber.
fuel combustion flue gases using the CO2CPU process could be applied. - The use of purified CO2 can make the design more economical.
The primary findings are summarized as follows: Therefore, using the product of this unit in a process is another
challenge that should be considered. Currently annual CO2 utiliza
- Oxy-fuel combustion can be easily retrofitted to the existing power tion to global anthropogenic CO2 production is lower than 1% which
generation system and CO2 can be capture easily using CO2CPU with is roughly negligible [221]. However many efforts have already been
high efficiency that removed challenges associated with chemical made in this regard, besides suggestions made to change the struc
solvents or physical sorbents and remains a promising decarbon ture of the process and examine its retrofit [222].
ization approach and further development is recommended. - Although fossil-fueled power plants are regarded as the largest
- Combustion performance varies in accordance with the type and sources of CO2 emission (about 0.888 kg CO2/kWh for coal fired
properties of the used fuel, oxygen purity in oxy-fuel combustion, power plant [223]), CO2 emitted from the cement industry accounts
thermo-physical properties of dilutions, and turbulence premixed for 5% of global annual emissions and 30% of annual industrial
oxy-fuel flue gases. In addition, the composition and operating emissions [224]. The process emits about 900 kg CO2/t of cement
conditions of the flue gas recycle affect the purity, recovery, and produced by current procedure [225]. As well as, because of the
energy consumption of both combustion chamber and CO2CPU sys expected growth in population and global demand for concrete as the
tem. Furthermore, energy consumption to O2 generation and main material for construction, cement production is predicted to
compression and sequestration CO2 using CO2CPU process is regar increase by 0.8–1.2% per year, reaching to 3.7–4.4 Gt in 2050 [14].
ded to be the biggest challenge in this technology. Therefore, a However, little research has been done on capturing CO2 from the
sensitivity analysis on above mention parameters and simultaneous cement industry and integrated CO2CPU system with cement in
multi-objective optimization is necessary for integrated optimization dustry is necessary.
of the process and acquisition of optimal values for the above vari - Finally, a necessity is felt for optimizing and investigating the dy
ables. Furthermore, plantwide control is required to ensure that the namic behavior of integrated oxy-fuel combustion system, including
process is feasible. boiler and turbine with downstream parts, i.e., dehydration, desul
- The effect of different impurities on the phase equilibrium and phurization, ASU and CPU units, seem to be necessary. Because any
corrosion in CO2CPU system and dynamic behavior of overall pro upstream disturbance regarding different operating scenarios has a
cess especially cold-box and separators is vital. Furthermore, pres direct effect on the performance of other units. Therefore, more
ence of impurities may affect design of process and equipment research should be done on the effects of these disturbances on the
specification such as compressor or pump power. Therefore sensi subsystems’ performance and integrated system.
tivity analysis of these impurities on equipment design and specifi
cation also are required. Declaration of Competing Interest
- Combination process of CO2CPU with other separation technology
such as absorption, membrane, and etc. may be increase perfor The authors declare that they have no known competing financial
mance of this process and recommended for more investigation. interests or personal relationships that could have appeared to influence
- The results show that when the CO2 pipeline leaks, since it is heavier the work reported in this paper.
than air and it diffuses much slower than natural gas, and accumu
lates near the ground which will be a massive threat [219]. References
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Review On Oxy Combustion

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Journal of Environmental Chemical Engineering 9 (2021) 105777

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

Review on principles, recent progress, and future challenges for oxy-fuel

2018, annual CO2 production reached 33.5 Gt and have grown by an

Nomenclature Greek letters

also to review the principles, latest advances, bottlenecks of this process

Fig. 1. The contributions of the primary source of CO2 emission.

2. Carbon capture and storage 3. The oxy-fuel combustion

Fig. 3. Block diagram of main combustion CO2 capture technology.

Efficiency penalty 7–10 [27] 8–12 [28] 7–11 [29]

Fig. 4. Number of studies vs. year.

transported via a pipeline (dense phase) or by ships, rail, and trucks

Since reduced impurity of CO2 product stream decreases operational

Fig. 7. Percentage deviation of thermodynamic properties due to impurities.

Fig. 8. Exhaust NOX and SO2 emissions in different combustion systems.

Fig. 9. Schematic figure of a pressurized oxy-combustion systems equipped with CO2CPU.

Cold Box 1 Duty (MW) 5.108 27.525 56.858

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