Energy 203 (2020) 117876

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Energy
journal homepage: www.elsevier.com/locate/energy

Optimal design, thermodynamic, cost and CO2 emission analyses of

coal-to-methanol process integrated with chemical looping air
separation and hydrogen technology
Dongqiang Zhang a, Runhao Duan a, Hongwei Li a, Qingchun Yang b, Huairong Zhou a, *
a
College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou, 730050, PR China
b
School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei, 230009, PR China

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

Article history: In China, coal is the main raw material used for methanol production to relieve the domestic supply and
Received 23 January 2020 demand. The conventional coal-to-methanol (CTM) process suffers from less energy efficiency since high
Received in revised form energy consumption of air separation and CO2 capture. A novel CTM process integrated with chemical
26 April 2020
looping air separation (CLAS) and chemical looping hydrogen (CLH) is designed and analyzed to reduce
Accepted 13 May 2020
Available online 18 May 2020
energy consumption, CO2 emission, and improve energy efficiency. The integration of CLAS technology
can remove air separation unit and decrease energy consumption to a certain extent. The integration of
CLH technology can remove water-gas shift unit and increase the CO2 concentration and reduce the
Keywords:
Coal-to-methanol
energy consumption of CO2 capture. The CLH technology also produces hydrogen used for adjustment of
Chemical looping air separation hydrogen to carbon ratio of the syngas. Process modelling results show that the energy consumption of
Chemical looping hydrogen the CLAS and that of the CO2 capture of the CLH are decreased by 41% and 89%, comparing to those of the
Process modelling conventional air separation and CO2 capture of the CTM process. In addition, the energy efficiency of the
Thermodynamic analysis new process is increased by 18% and CO2 emission reduced by 45% in comparison with the conventional
CTM process.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction China [3e5].

The flow diagram of the conventional CTM process is shown in
Methanol and methanol derivatives are widely used in the Fig. 2 [6]. This process contains five central units: cryogenic air
petrochemical and energy industries. In recent years, China has separation (CAS), coal gasification (CG), water-gas shift (WGS), acid
become the largest methanol producer and consumer in the world gas removal (AGR) and methanol synthesis and distillation (MSD).
[1,2]. Fig. 1 shows the comparison of China’s methanol production After grinding and drying, the coal is sent to the crusher to be
capacity with global capacity. The global methanol production ca- pulverized and then mixed with water to form a coal-water slurry.
pacity is increasing, and that of China is also increasing. In addition, The coal-water slurry enters the gasifiers and reacts with oxygen
the proportion of China’s methanol production capacity in the from the CAS unit to produce syngas. Part of the crude syngas en-
world is increasing. For example, the methanol capacity of China ters the WGS unit to convert CO to H2 and CO2. The shift gas from
accounted for 59.3% of the global methanol capacity in 2018. The the WGS unit is mixed with the other crude syngas and is sent to
main raw materials for methanol production include crude oil, the AGR unit to remove CO2 and H2S. The clean syngas from the
natural gas, coal, and biomass. In China, the energy structure is rich AGR unit satisfies the carbon to hydrogen ratio of 2.0e2.2 and is
in coal, poor in oil and little in natural gas. Coal-to-methanol (CTM) sent to the MSD unit to produce methanol [7,8].
as an alternative method is very important for methanol produc- As described above, the conventional CTM process contains the
tion in China. According to statistics, the methanol capacity of the CAS unit, and cryogenic air separation technology has been widely
CTM process accounts for 58% of the total methanol production in used to produce oxygen in industry. However, the CAS unit has a
large energy consumption during oxygen separation. To obtain a
purity of 95% oxygen, the energy consumption is approximately
* Corresponding author. 200 kWh/t O2 [9]. Additionally, the conventional CTM process
E-mail address: [email protected] (H. Zhou). contains the WGS unit and the AGR unit with the aim of adjusting

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2 D. Zhang et al. / Energy 203 (2020) 117876

summary, the main problems of the conventional CTM process are

Nomenclature the large energy consumption of the air separation unit and the CO2
capture from the AGR unit, which leads to the low energy efficiency
of the process [11,12]. The current research aims to solve these
Greek letters problems and improve the energy efficiency.
l₁ split ratio Due to the high reliability of the cryogenic air separation tech-
l₂ recycling ratio nology, it is difficult to reduce the energy consumption based on the
u carbon utilization rate original technology. Therefore, alternative technologies with low
d₁ total process energy efficiency of without CO2 energy consumption have been studied by many researchers.
capture Chemical looping air separation (CLAS) technology has attracted
d₂ total process energy efficiency of with CO2 capture extensive attention because of its significant advantages for highly
efficient pure oxygen production with low energy consumption and
Abbreviations low capital investment. A series of experiments and modelling
CTM coal-to-methanol studies on CLAS technology have been carried out by researchers at
CTMCLAS&H coal-to-methanol process integrated with Newcastle University. It is concluded that CLAS technology has
chemical looping air separation and hydrogen great potential to replace traditional CAS technology [13]. There are
technology other studies about integrating CLAS technology into chemical
CLH chemiacal looping hydrogen generation processes. [14] developed several oxygen-fuel thermal power
CLAS chemiacal looping air srparation plants with integrated CLAS and found that CLAS technology can
CG coal gasification reduce the energy loss by 3e4% and reduce the operating cost of
MSD methanol synthesis and distillation oxygen production. [15] proposed a new technology to integrate
steam/(FeO þ Fe) steam/(FeO þ Fe) mass ratio coal gasification with CLAS technology from the perspective of
Fe2O3/crude syngas Fe2O3/crude syngas molar ratio thermodynamics and found that CLAS had lower energy loss than
O2/coal O2/coal mass ratio other oxygen production technologies. [16] developed a process of
air/Mn3O4 air/Mn3O4 mass ratio coal gasification for power generation integrated with CLAS tech-
steam/Mn2O3 steam/Mn2O3 molar ratio nology. However, the researches on CLAS technology integrated
with CTM are relative found by the best knowledge of the authors.
The energy consumption of CO2 capture is influenced by the
concentration of CO2 in the flows. Chemical looping hydrogen
production (CLH) technology can effectively increase the concen-
tration of CO2 and produce hydrogen [17e19]. At the Ohio State
University, a 25 kWth pilot CLH device was established, which
consists of three reactors: a fuel reactor, a reduced reactor and an
air reactor. Coal and syngas were used as materials in this device,
and the results showed that 99.99% hydrogen and 100% CO2 were
obtained [20]. In addition, a large number of researchers have
attained different achievements in CLH technology. [21] modelled
chemical looping hydrogen production, in which iron is used as an
oxygen carrier and coal is used as fuel. Based on the modelling and
simulation results, the CO2 capture rate can reach 95%. [22] pro-
posed a new integrated process of biomass gasification, CLH and
power generation, and CO2 capture. In this proposed process,
syngas from biomass gasification was used as the fuel, and CaO was
used as the oxygen carrier. After modelling and optimization, the
optimized process was achieved with a higher energy efficiency
Fig. 1. The comparison of China’s methanol production capacity with global capacity.
and zero CO2 emissions. [23] investigated the CLH technology used
for the conversion of coke oven gas into hydrogen. Based on the
the hydrogen to carbon ratio for methanol production. In this sit- optimized simulation, their results showed that the purity of
uation, a large amount of CO2 is generated. Nevertheless, the shift hydrogen was 99.4% and the CO2 capture rate was 100%. However,
gas is mixed with the unshifted gas before entering the AGR unit for the researches on the CLH technology integrated with CTM are also
CO2 removal, which results in a low concentration of CO2 and a high rare.
energy consumption of CO2 capture in the AGR unit [10]. In The CLAS technology compared with the conventional CAS

Fig. 2. Flow diagram of the traditional CTM process.

 D. Zhang et al. / Energy 203 (2020) 117876 3

technology has advantages in lower energy consumption of oxygen Table 1

production. In addition, the CLH technology has advantages in Main operating parameters of the CTMCLAS&H process.

lower energy consumption of CO2 capture and production of Unit Parameter Value
hydrogen in comparison with conventional WGS and AGR units. CGa Pressure (MPa) 6.5
Based on the above description, a new CTM process integrated with Temperature ( C) 1300e1500
the CLAS and CLH technologies (CTMCLAS&H) is proposed in this Oxygen/coal mass ratio 0.7
paper. The new process aims to adopt the CLAS technology to Coal-water slurry molar fraction 65
CLASb Oxygen carrier Mn2O3
replace the conventional CAS unit to provide oxygen for coal gasi-
Steam/Mn2O3 0.3
fication, and the CLH technology is used to replace the conventional Pressure (MPa) 0.1
WGS and AGR units to provide hydrogen for adjustment of syngas Temperature ( C) 800e900
composition, as well as capture CO2 with a low energy consump- CLHc Oxygen carrier Fe2O3
Fuel reactor and steam reactor pressure (MPa) 2
tion. In the following Section of this paper, first, the description of
Air reactor pressure (MPa) 1
the proposed process and modelling and simulation are imple- Temperature ( C) 900
mented. Then, the key operation parameters and process parame- MSDd Catalyst Cu/ZnO/Al2O3
ters are investigated. Finally, the technical performance and CO2 Pressure (MPa) 7
emission of the new process are analyzed, and a comparison with Temperature ( C) 250
Recycling ratio 0.85
the conventional CTM process is also conducted to demonstrate the
PGe Gas turbine inlet temperature ( C) 1200
advantages of this proposed process. Pressure ratio 13
Isentropic efficiency (%) 90
2. Process description, modelling and simulation a
Chen et al., 2010; Zhu et al., 2016.
b
Zhou et al., 2015; Cormos, 2017.
c
The flow diagram of the newly proposed CTMCLAS&H process is d
Tong et al., 2014; Mehrpooya et al., 2017; Xiang and Zhou, 2018.
Parle et al., 2014; Bussche and Froment, 1996.
shown in Fig. 3. This new process mainly consists of the CG, CLAS, e
Shi et al., 2018; Demirel et al., 2015.
CLH, MSD and power generation (PG) units. The CLAS unit is used
for the production of oxygen, and then oxygen is sent to the CG unit
to be reacted with coal to produce syngas. The crude syngas from Table 2
the CG unit is cooled by the waste heat boiler, and then the syngas is Proximate analysis and ultimate analysis of raw coal.
divided into two parts: one part of the syngas is sent to the CLH unit Proximate analysis (wt.%, ad) Ultimate analysis (wt.%, ad)
for simultaneous hydrogen production and CO2 capture. The
M FC V A C H O N S
hydrogen from the CLH unit is mixed with the other syngas, and the
mixture enters the MSD unit for methanol synthesis. Part of the Coal 6.10 50.01 24.71 19.18 66.31 4.43 8.50 0.76 0.82

unreacted gas from the MSD unit is compressed and recirculated

into the MSD unit to continually synthesize methanol. The
remaining unreacted gas is burned to generate steam, and the decompose coal into C, H2, N2, O2, S, and ash contents at a tem-
steam is used for power generation. The key operation parameters perature of 500  C and pressure of 6.5 MPa [25]. The main equa-
of this new process are shown in Table 1. tions of the gasification process is shown as follows [26]:

2.1. Coal gasification unit C þ H2O / CO þ H2 DH ¼ þ131.4 kJ/mol (1)

Due to the complex composition of coal, it is necessary to CO þ H2O / CO2 þ H2 DH ¼ 42.0 kJ/mol (2)
conduct an industrial analysis of coal to define its elemental con-
stituents, as shown in Table 2. In addition, the components in Aspen C þ CO2 / 2 CO DH ¼ þ172.6 kJ/mol (3)
Plus (Version 9.0) are defined as the unconventional components;
HCOALGEN is adopted for the enthalpy model, and DCCOALIGN is C þ 2H2 / CH4 DH ¼ 75.0 kJ/mol (4)
adopted for the density model.
The Texaco coal-water slurry gasification technology was The gasification process adopts the RGibbs model, which mini-
adopted in coal gasification [24]. During the modelling of coal mizes Gibbs free energy, and the physical property method in the
gasification, two independent processes are assumed, the pyrolysis coal gasification modelling process is the Peng-Rob model. For the
process and the gasification process, which uses RYield reactor to CG unit, the O2/coal mass ratio parameter must be optimized. The

Fig. 3. Flow diagram of the CTMCLAS&H process.

4 D. Zhang et al. / Energy 203 (2020) 117876

O2/coal mass ratio has an effect on the molar flow rate of the main ratio. Fig. 5 shows the effect of the different mass ratios of the
components in the crude syngas and the temperature of the conversion rates of Mn3O4 and oxygen. The oxygen conversion rate
gasifier. The optimized results are shown in Fig. 4. With an increase decreases, while that of Mn3O4 increases with increasing air/Mn3O4
in the O2/coal mass ratio, the molar flow rates of CO and H2 first mass ratio. When the air/Mn3O4 mass ratio increases from 0.05 to
increase and then decrease, while the molar flow rates of H2O and 0.1, the oxygen conversion rate decreases significantly. Excess
CO2 constantly increase. When the O2/coal mass ratio reaches 0.7, Mn3O4 accelerates the reaction and oxygen absorption to be con-
the molar flows of CO and H2 reach their maximum values. In verted into Mn2O3 for recycling. When the air/Mn3O4 mass ratio
addition, the temperature of the gasifier is increased prominently increases from 0.1 to 0.2, the oxygen conversion decreases slowly,
as the increase in the O2/coal mass ratio increases. This is because and the conversion trends remain constant as the air/Mn3O4 mass
an increase in the O2/coal mass ratio indicates an increase in oxygen ratio exceeds 0.2. Therefore, the air/Mn3O4 mass ratio is deter-
entering the gasifier, which will aggravate the reactions in the mined to be 0.2.
gasifier. More CO and H2 in the gasified syngas will be burned to For the reduction reactor, the key parameter is steam/Mn3O4
CO2 and H2O, and the reaction heat leads to a continuous increase mass ratio. Fig. 6 shows the change in the Mn2O3 conversion rate
in the temperature of the gasifier. In practice, more CO and H2 are with the steam/Mn2O3 molar ratio at different reaction tempera-
required in the syngas, and the temperature of the gasifier is tures. At the same temperature, with the increase in the steam/
required to be between 1300 and 1500  C. Therefore, considering Mn2O3 molar ratio, the Mn2O3 conversion rate shows an increasing
the above conditions, the O2/coal mass ratio is set to 0.7. trend and then reaches a reaction equilibrium. Under the same
steam/Mn2O3 molar ratio, the Mn2O3 conversion rate increases
2.2. Chemical looping air separation unit with increasing temperature. Because the reaction of steam and
Mn2O3 for the production of oxygen is an endothermic reaction, a
The CLAS technology separates oxygen from air by oxidation- higher temperature will promote the reaction. Consequently,
reduction reactions between two interconnected reactors with considering that the Mn2O3 conversion rate reaches above 99%, the
oxygen carriers [27]. The CLAS technology contains two core re- reaction temperature is chosen to be 830  C, and the steam/Mn2O3
actors: an oxidation reactor and a reduction reactor. In the OR, the molar ratio is chosen to be 0.3.
oxygen carrier reacts with air to carry oxygen. The oxidized oxygen
carrier from the oxidation reactor is sent to the reduction reactor to 2.3. Chemical looping hydrogen production unit
be reduced by steam/CO2 to regenerate oxygen. The reduced oxy-
gen carrier is circulated into the oxidation reactor for oxidation and Part of the gasified syngas is used for hydrogen production and
carrying oxygen. The oxygen carriers mainly include CuO/Cu2O, CO2 capture with low energy consumption by the CLH technology.
CoO/Co3O4, MnO2/Mn2O3 and Mn2O3/Mn3O4 [28]. In this model- The CLH technology consists of three core reactors: the fuel reactor,
ling, Mn2O3/Mn3O4 is selected as the oxygen carrier because of its the steam reactor and the air reactor. The syngas first enters from
higher reaction performance under mild conditions compared with the bottom of the fuel reactor, and the oxygen carrier enters from
other oxygen carriers [29]. The reaction taking place in the oxida- the top of the fuel reactor, where the syngas is burned into CO2 and
tion reactor is shown in Eq. (5), H2O and the oxygen carrier is reduced. The mixture from the fuel
reactor is sent to the cyclone separator to be separated into gas- and
4 Mn3O4 þ O2 / 6 Mn2O3 (5) solid-phase flows. The gas-phase flow is condensed, and water is
separated from the gas-phase flow. Then, the remaining gas-phase
Steam is introduced into the reduction reactor to react with the flow has a high concentration of CO2, which can be easily captured
oxidized oxygen carrier. The main reaction is shown in Eq. (6), with low energy consumption [30]. The solid-phase flow from the
cyclone separator is the reduced oxygen carrier. The reduced oxy-
6 Mn2O3 / 4 Mn3O4 þ O2 (6) gen carrier enters the steam reactor and reacts with the introduced
steam to produce hydrogen, and the reduced oxygen carrier is
For Aspen Plus modelling, the oxidation reactor and reduction partially oxidized. The outlet mixture is introduced to another
reactor are modelled by the RGibbs model with Gibbs free energy cyclone separator to separate the hydrogen and partially oxidized
minimization. In addition, the Peng-Rob model is selected as the oxygen carriers. The hydrogen is mixed with the other portion of
physical property method. the syngas to adjust the hydrogen to carbon ratio for methanol
For the oxidation reactor, the key parameter is air/Mn3O4 mass

Fig. 4. Influence of O2/coal on the molar flow of syngas and the gasifier temperature. Fig. 5. The influence of different air/Mn3O4 ratios on the conversions of Mn3O4 and O2.
 D. Zhang et al. / Energy 203 (2020) 117876 5

Fig. 7. Effect of Fe2O3/crude syngas on the changes in syngas and heat duty of fuel
reactor.

Fig. 6. The Mn2O3 conversion rate changes with the steam/Mn2O3 molar ratio.

Fig. 8 shows the effects of different steam/(Fe þ FeO) mass ratios on

production. The partially oxidized oxygen carrier is sent to the air the conversion rates of steam, FeO, and Fe and on the molar flow
reactor and reacts with the O2 in the air to become completely rate of hydrogen production. The FeO conversion rate does not
oxidized. The oxidized oxygen carrier is circulated into the fuel change. In the fuel reactor, Fe2O3 reacts with excess syngas (Eq.
reactor to supply oxygen for syngas combustion. (3,4)) to produce FeO, and FeO reacts with the remaining syngas to
Previous investigations of oxygen carriers were mainly focused produce Fe. When the steam/(Fe þ FeO) ratio increases from 0.1 to
on Ni-based, Cu-based, Fe-based, Mn-based and Cr-based oxygen 0.7, the Fe conversion rate and the H2 molar flow rate continue to
carriers. The Fe-based oxygen carrier has good reactivity and low increase. When the steam/(Fe þ FeO) ratio is equal to 0.7, the Fe
cost when it is used as a material. Therefore, a Fe-based oxygen conversion rate can reach 0.91. FeO always has a conversion rate of
carrier is selected as the oxygen carrier [31]. The main reactions 0.99. As the steam/(Fe þ FeO) ratio increases from 0.7 to 0.9, the Fe
occurring in the fuel reactor are shown in Eqs (7).-(10), conversion tended to remain constant. With the increase in the
steam/(Fe þ FeO) ratio, the steam conversion rate has been
Fe2O3 þ CO / 2 FeO þ CO2 DH ¼ 3.2 kJ/mol (7) decreasing. Therefore, the steam/(Fe þ FeO) ratio chosen for this
simulation is 0.7.
Fe2O3 þ H2 / 2 FeO þ H2O DH ¼ þ32.4 kJ/mol (8)

FeO þ CO / Fe þ CO2 DH ¼ 10.9 kJ/mol (9) 2.4. Methanol synthesis unit

FeO þ H2 / Fe þ H2O DH ¼ þ 30.2 kJ/mol (10) The syngas, with a hydrogen to carbon ratio of 2, enters the MSD
unit for methanol production. Methanol synthesis reactions occur
The oxygen carrier Fe2O3 is reduced to FeO and Fe in the fuel on the Cu-based catalyst, and the reactions are shown in Eqs
reactor, and they are partially oxidized to Fe3O4 in the steam reactor (14,15). [32],
as follows:
CO þ 2H2 / CH3OH DH ¼ 90.64 kJ/mol (14)
3 FeO þ H2O / Fe3O4 þH2 DH ¼ 59.3 kJ/mol (11)
CO2 þ 3H2 / CH3OH þ H2O DH ¼ 49.47 kJ/mol (15)
3 Fe þ 4H2O / Fe3O4 þ 4H2 DH ¼ 149.9 kJ/mol (12)
The corresponding kinetic models are shown in Eq (16). [33],
The Fe3O4 from the steam reactor reacts with oxygen and is
completely oxidized to Fe2O3, as follows:

4 Fe3O4 þ O2 / 6 Fe2O3 DH ¼ 471.9 kJ/mol (13)

For Aspen Plus modelling, the fuel reactor, steam reactor and air
reactor are modelled by the RGibbs model with Gibbs free energy
minimization. In addition, the Peng-Rob model is selected as the
physical property method.
For the fuel reactor, the input of Fe2O3 is modelled. Fig. 7 pre-
sents the influence of different Fe2O3/crude syngas molar ratios on
the conversion of syngas and on the fuel reactor heat duty. The
molar flows of CO and H2 in the crude syngas decrease, while those
of CO2 and H2O increase with the increase in the Fe2O3/crude
syngas molar ratio. When the Fe2O3/crude syngas molar ratio rea-
ches 0.3, the CO and H2 in the crude syngas are nearly all converted
into CO2 and H2O. Therefore, the Fe2O3/crude syngas molar ratio is
determined to be 0.3 in this paper.
Fig. 8. Influence of the steam/(FeO þ Fe) ratio on the conversion rate of steam, FeO,
For the steam reactor, the consumption of steam is modelled. and Fe and on hydrogen production.
6 D. Zhang et al. / Energy 203 (2020) 117876

[16]

For Aspen Plus modelling, the methanol synthesis reactor is

modelled by the RPlug model. In addition, the SRK model is
selected as the physical property method.

2.5. Process simulation

There are two operational parameters in the studied processes

[1]: the split ratio l1, the ratio of the crude syngas from the CG unit
to the CLH unit [2]; the split ratio l2, the ratio of the recycle gas flow Fig. 10. Influence of split ratio l2 on methanol production and power consumption of
at the output of the MSD unit. Fig. 9 shows that the split ratio l1 has the MSD.
an effect on the hydrogen to carbon (H/C) ratio of syngas and
methanol synthesis. The H2 molar flow in the syngas increases,
while that of CO decreases as the split ratio l1 increases. When Cmeth
increasing the split ratio l1, more CO is converted into H2 and CO2. u¼ (17)
Ccoal
However, the CO2 molar flow in the syngas before methanol syn-
thesis is basically the same. When the split ratio l1 is 0.5, the H/C where u is the utilization rate of elemental carbon, Cmeth is the
ratio reaches 2.0, and the production of methanol reaches its elemental carbon molar flow rate in methanol, and Ccoal is the
maximum. Therefore, the split ratio l1 is set at 0.5 in this paper. carbon in coal molar flow.
Fig. 10 shows the effect of the split ratio l2 on the production of Fig. 11 compares the CTM process with the CTMCLAS&H process of
methanol and the energy consumption of the compressor. With the methanol production and utilization of carbon. The elemental
increase in the split ratio l2, the production of methanol and energy carbon molar flow into the input system is 10938.20 kmol/h, the
consumption are increasing. When the split ratio l2 is more than elemental carbon molar flow into the methanol unit is
0.85, the production of methanol increases slowly, while that of the 4573.71 kmol/h with a final amount of 4040.12 kmol/h of methanol
energy consumption for the circulation of unreacted syngas in- produced, the carbon utilization rate was 37.0%, and the unused
creases significantly. Increasing the split ratio l2 will increase part of carbon flowed into the CO2 removal unit. This part of the
methanol production, but the increase in power consumption is carbon accounts for 49% of the elemental C in the input system. The
greater than that of the methanol output. Therefore, the split ratio traditional process finally obtained 3907.89 kmol/h methanol, and
l2 is determined to be 0.85. the carbon utilization rate was 35.7%. Compared with the tradi-
Based on the above analysis, the whole process of the tional process, the new process does not significantly improve the
CTMCLH&CLA is simulated, and the simulation results are obtained utilization rate of elemental carbon. If the utilization rate of the
and shown in Table 3. The corresponding stream number is referred elemental carbon is to be improved, it needs to supplement the
to in Fig. 3. external hydrogen process; thus, the syngas flows into the
hydrogen production units needs to be reduced, which would
improve the flow of the carbon methanol synthesis unit, improve
methanol production, and increase the carbon utilization rate. This
3. Thermodynamic analysis
process does not involve a hydrogen source; therefore, it is the
same as traditional carbon utilization.
3.1. Carbon utilization rate

Carbon utilization is an essential indicator for examining the 3.2. Energy consumption for oxygen production
CTM and CTMCLAS&H processes, which can be defined by Eq. (17),
As an important index for the analysis of the CLAS process in this
paper, the oxygen production energy consumption can be
expressed by Eq. (18),

Eair þ Eutil
f¼ (18)
FO2

where Eair represents the energy of the input air; Eutil represents the
utility energy input to the air separation unit, and for the chemical
looping air separation, this term represents water vapor. For cryo-
genic air separation, including the power required for air
compression cycle refrigeration; FO2 is the mass flow of oxygen.
Fig. 12 shows the comparison of energy consumption of the
CLAS with traditional CAS. The diagram shows that the oxygen
consumption of the CLAS unit is 0.24 GJ/t, and the oxygen con-
sumption of the CAS unit is 0.41 GJ/t; compared with the energy
consumption of the CAS unit, the energy consumption of the CLAS
Fig. 9. Influence of the split ratio l1 on the syngas compositions and H/C ratio. unit was reduced by 40.7% because the CAS unit needs compressed
 D. Zhang et al. / Energy 203 (2020) 117876 7

Table 3
Main logistics and simulation data of the CTMCLAS&H process.

Stream No. 1 2 3 4 5 6 7

Molar fraction (%)

CO e 40.09 0.19 e 54.41 30.84 10.71
CO2 e 9.11 91.49 e 2.49 1.41 5.93
H2 e 29.89 0.09 98.84 41.33 66.23 81.49
H2O e 20.48 7.35 1.16 1.42 1.31
N2 e 0.18 0.47 e 0.35 0.21 1.41
H2S þ SOx e 0.25 0.41 e e e e
CH3OH e e e e e e 0.46
Molar flow (kmol/h) e 22258.12 5871.07 6148.65 8042.37 14191.21 1718.88
Temperature ( C) 40 1354 40 40 200 125 40
Pressure (MPa) 0.1 6.5 0.1 3.0 6.5 6.5 7.0

of gases, which can be calculated from Eq (19). [34e35],



xCO2 ln xCO2 þ 1  xCO2 ln 1  xCO2
Wsep ¼  RT0 Fsep (19)
xCO2 hsep

where R is the molar gas constant equal to 8.314 J/(mol$K); T0 is

298.15 K; xCO2 is the concentration of carbon dioxide in the sepa-
ration gas; and Fsep is the molar flow rate of the gas to be separated;
hsep is used for the separation efficiency. It is important to note that
this formula is based on the assumption that the composition of the
gas mixture is a binary mixture of CO2 and gases other than CO2
(treated as inert components).
Fig. 13 shows the energy consumption of CO2 capture in the CTM
and CTMCLAS&H processes under the same separation efficiency
(hsep). The value of the hsep is assumed to be 0.3 according to
Ref. [34]. As seen from the figure, the CO2 capture energy con-
sumption of the CTM process is 1.18 GJ/t, while that of the
Fig. 11. Carbon efficiencies of the CTM and CTMCLAS&H processes.
CTMCLAS&H process is only 0.13 GJ/t, which is 89.0% lower than that
of the CTM process. From the Eq. (19), the main parameters influ-
encing CO2 capture energy consumption are the CO2 concentration
before separation and separation efficiency. This analysis adopts
the same separation method, and the separation process efficiency
is the same. The concentration of CO2 before the separation of the
CTMCLAS&H process is reached 91.5%, while that of the CTM process
before the separation is 29.5%. The mixture flows from the fuel
reactor in the CLH unit of the CTMCLAS&H process with high CO2

Fig. 12. Comparison of the energy consumption between the CLAS and CAS units.

air cycle refrigeration and separation. This process requires

considerable power and large energy consumption during the
process of operation; the CLAS unit mainly consumes steam, and
most of the heat is provided by the exothermic oxidation of the
oxygen carrier, which greatly reduces the energy consumption.

3.3. Energy consumption for CO2 capture

The energy consumption of CO2 capture is an important indi-

cator for analysis in this paper. The CO2 capture studied in this
paper can be regarded as the case of the gas separation. Therefore,
the minimum energy consumption of CO2 capture is the minimum Fig. 13. Comparison of energy consumption for CO2 capture in the CTM and
work required to separate the target component from the mixture CTMCLAS&H.
8 D. Zhang et al. / Energy 203 (2020) 117876

concentration, then flows to the separation unit; the CO2 concen- Table 5
tration before separation is 3.1 times that of the traditional process. Utility input energy of the CTMCLAS&H and CTM.

Therefore, the energy consumption of CO2 capture in the Item (MW) CTMCLAS&H CTM
CTMCLAS&H is decreased by 89.0% than that in the CTM process. CAS e 95.30
CLAS 52.10 e
CG 57.81 58.43
CLH 68.93 e
3.4. Energy efficiency
WGS e 89.21
AGR and CO2 capture 29.54 77.50
Energy efficiency is an important indicator for comparing the MSD 35.40 45.30
CTM process with the CTMCLAS&H process. This paper examines the
energy efficiency of the CTM process with and without the CO2
capture unit and that of the CTMCLAS&H process. The calculation of
the energy efficiency of the section without and with CO2 capture
are defined by formulas (20,21) [36],

Eout
d1 ¼ (20)
Ecoal þ Eutil

Eout
d2 ¼ (21)
Ecoal þ Eutil þ ECO2

where d1 and d2 represents the energy efficiency of the system

without and with adding the CO2 capture unit; Eout represents the
sum of energy of the product and output power; Ecoal is the energy
of coal; Eutil represents the energy input of utilities (including steam
and electricity), and ECO2 represents the energy input of capturing
CO2. Corresponding input and output data are shown in Table 4 and
Table 5. Fig. 14. Energy efficiencies of the CTM and CTMCLAS&H processes.
The energy efficiency of the CTMCLAS&H process with the same
coal intake is compared with that of the traditional CTM process.
Fig. 14 shows the energy efficiency of the CTMCLAS&H process 4. Cost analysis
without and with the CO2 capture unit. The energy efficiency
without adding CO2 capture of the CTMCLAS&H process is 54% and The product costs of the CTM and CTMCLAS&H processes are
that of the traditional process is 47.3%, and the energy efficiency of calculated referred to our previous work [37]. For calculation of
the CTMCLAS&H is increased by 14.1%. The increase in energy effi- product cost, we adopt 4% of salvage rate and 15 years of depreci-
ciency is mainly because of the application of the CLAS for sup- ation. The prices of coal, steam, electricity, and methanol are set to
plying oxygen instead of the CAS in the CTMCLAS&H. In addition, 88.6 US$/t, 6.0 US$/GJ, 0.1 US$/kWh, and 328.6 US$/t, respectively.
moderating circulation to reduce the energy consumption of the The exchange rate of US dollar and RMB is set as 1 US$ ¼ 7.0 RMB.
compressor and diverting part of the gas to generate power in the After calculation, the product costs of the CTM and CTMCLAS&H
PG unit of the CTMCLAS&H. The thermal power plant is replaced with processes are 272.6 US$/t and 264.0 US$/t, as shown in Fig. 15. The
a waste heat boiler, and the high-temperature syngas flowing product cost of the novel process (CTMCLAS&H) is 3.2% lower than
through the waste heat boiler is part of the heat recovery. After the that of the conventional CTM process. The lower utilities con-
production of the high-pressure steam for turbine power genera- sumption and higher methanol production make the new process
tion, the power provides a part of the electric power system, re- more cost effective. In addition, the payback period of these two
duces the consumption of common engineering, and further processes is calculated. The payback period of the CTMCLAS&H pro-
reduces the energy loss. Compared to the energy efficiency with the cess is 5.2 years, which is lower than that of the conventional CTM
CO2 capture, the energy efficiency of the CTMCLAS&H process is process (7.2 years), as shown in Fig. 15.
reached 53.7% and that of the traditional CTM process is 45.5%, and
the energy efficiency is increased by 18.0% for the CTMCLAS&H. Due
to the CO2 capture, the energy consumption will increase, and the
change in the energy efficiency of the process is bigger in the CTM;
while the CO2 capture in the CTMCLAS&H process producing a high
CO2 concentration, it greatly reduces the energy consumption of
the CO2 capture and the process efficiency change is not obvious.

Table 4
Coal input and methanol and power output of the CTMCLAS&H and CTM.

Item CTMCLAS&H CTM

Input
Coal (t/h) 215.00 215.00
Raw water (t/h) 524.50 508.40
Output
Methanol (t/h) 129.45 112.71
Power (MW) 60 e
Fig. 15. Product costs of the CTM and CTMCLAS&H processes.
 D. Zhang et al. / Energy 203 (2020) 117876 9

The remaining unreacted gas is used for power generation to pro-

vide part of the power consumption of the CTMCLAS&H process.
2. The energy consumption of the chemical looping air separa-
tion unit in the CTMCLAS&H process is 0.24 GJ/t O2, which is
decreased by 41% compared with the conventional cryogenic air
separation unit in the CTM.
3. The chemical looping hydrogen unit in the CTMCLAS&H can
produce hydrogen to adjust hydrogen to carbon ratio of the syngas
and supply a higher concentration of CO2. The energy consumption
of CO2 capture of the CTMCLAS&H process is 0.13 GJ/t CO2, which is
reduced by 89% compared with that of the conventional CTM.
4. The energy efficiency of the CTMCLAS&H process is 54.0% and
53.7% without and considering the energy consumption of CO2
capture. The energy efficiency is increased by 14% and 18% in
comparison to that of the conventional CTM process when the
energy consumption of CO2 capture is not considered or is
considered.

Fig. 16. CO2 emission of the CTM and CTMCLAS&H processes. 5. The product cost and payback period of the CTMCLAS&H process
are 260 US$/t and 5.2 years, 3.2% and 2 years lower than that of
the conventional CTM.
5. CO2 emission analysis 6. The CO2 emission of the CTMCLAS&H process is 2.94 t/t methanol,
which is reduced by 45% compared to that of the conventional
The calculation of CO2 emission includes direct emission and CTM.
indirect emission, as shown in Eq (22). [38].

d ind d
P This study reveals that the integration of the chemical looping
ECO þ ECO ECO þ ECj  pj;CO2
ECO2 ¼ 2 2
¼ 2
(22) air separation and chemical looping hydrogen technologies can
mpro mmeth remove the conventional cryogenic air separation unit and water-
d ind present the direct emission and indi-
gas shift unit, which significantly reduces energy consumption,
In Eq. (22), ECO and ECO
2 2 CO2 emission, and improve the energy efficiency of the CTM pro-
rect emission of the methanol production process; ECj is the utilities cess. In addition, this study also provides a solution for the utili-
consumption (steam and electricity) of the methanol production zation of the industrial-scale oxygen produced in the independent
process and pj,CO2 is the CO2 emission factor from process utilities chemical looping air separation technology and the industrial-scale
consumption. Based on the simulation data in Section 2 and the CO2 hydrogen produced in the independent chemical looping hydrogen
emission of the CTM and CTMCLAS&H processes is calculated by Eq technology, finally realized its process feasibility, magnification,
(22). and the result is shown in Fig. 16. The CO2 emission of the CTM and industrialization.
and CTMCLAS&H processes are 5.31 t/t-methanol and 2.94 t/t-
methanol, respectively. The CO2 emission of the CTMCLAS&H process Declaration of competing interest
is reduced by 44.63% compared that of the CTM process. It can be
seen obviously from Fig. 16, the reduction of CO2 emission of the The authors declare that they have no known competing
CTMCLAS&H process is mainly the indirect emission caused by financial interests or personal relationships that could have
electricity and stem consumption. CTMCLAS&H process adopts appeared to influence the work reported in this paper.
advanced CLAS and CLH technologies with low energy consump-
tion to replace the CAS and WGS and AGR in the conventional CTM CRediT authorship contribution statement
process, which greatly reduce the utilities consumption. Thus, it is
concluded that CO2 emission reduction is achieved by reducing Dongqiang Zhang: Validation, Writing - original draft. Runhao
process energy consumption and improving process energy Duan: Investigation, Methodology, Software. Hongwei Li: Re-
efficiency. sources, Supervision. Qingchun Yang: Writing - review & editing,
Supervision. Huairong Zhou: Investigation, Conceptualization,
6. Conclusions Writing - review & editing, Supervision, Project administration.

The conventional coal-to-methanol (CTM) process suffers from Acknowledgements

high energy consumption, which results in less energy efficiency
for methanol production. In this paper, a new process of the CTM The authors would like to thank the financial support from the
process integrated with chemical looping air separation and China NSF project (NO. 21666018).
chemical looping hydrogen (CTMCLAS&H) is proposed. The new
process has the advantages of low energy consumption of air sep- References
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