Journal of Cleaner Production 396 (2023) 136540

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Optimal integration design of sustainable ethylene glycol production

process considering economic benefit and environmental impact
Qingchun Yang a, b, *, Yingjie Fan a, Jianlong Zhou a, Lei Zhao a
a
School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei, 230009, PR China
b
Anhui HaoYuan Chemical Group Co., Ltd., Fuyang, 236023, PR China

A R T I C L E I N F O A B S T R A C T

Handling Editor: Panos Seferlis The requirement for ethylene glycol (EG) continues to surge owing to the booming demand for indispensable
platform materials. Unfortunately, there is limited insight into engineering modeling, process enhancement, and
Keywords: process optimization to achieve carbon neutrality in ethylene glycol production. Herein, four biomass-to-
Biomass to ethylene glycol ethylene glycol (BtEG) processes that integrate renewable energy for hydrogen production and CO2 utilization
Carbon neutral
are proposed to find the best strategy for the carbon-neutral and cost-effective development of the ethylene
Renewable energy
glycol industry. Rigorous steady-state modeling and simulation of the proposed BtEG processes with various
CO2 utilization
Techno-economic analysis gasification agents are conducted to investigate the effect of different gasification agents on the performance of
the BtEG processes. The technoeconomic and environmental performance of the proposed processes is assessed
and compared with the conventional process. Results show that the proposed BtEG processes can significantly
boost the system performance of the conventional process. The carbon utilization efficiency, exergy efficiency,
and internal rate of return of four proposed BtEG processes are improved by 38.96%–43.2%, 0.98%–7.13%, and
1.94%–11.28%, respectively. The environmental performance of the proposed BtEG processes is greatly superior
to that of the conventional process since the life cycle GHG emissions of the proposed processes are negative,
which are lower than − 1.47 t/t. Therefore, this study provides a sustainable and cost-efficient improvement
direction for the carbon-intensive ethylene glycol industries.

1. Introduction renewable energy and realizing energy transformation, which is from

Global warming has greatly accelerated due to the increase of the
depletion in fossil fuels, emitting a large number of greenhouse gases for
the past 30 years (Hernandez-Gomez et al., 2020). If the global tem­
perature rise reaches 2 ◦ C, 99% of coral reefs will vanish, and about 13%
of the ecological system on land will be destroyed (IPCC, 2021).
Consequently, countries across the world endeavor to cut down the
emissions of greenhouse gases and mitigate global warming. For
example, the Paris Agreement proposed the goal of achieving net zero
emissions in the second half of this century in 2015. China pledged to
reach a carbon peak by 2030 and become carbon neutral by 2060 (Zhao
et al., 2022). As the Energy & Climate Intelligence Unit reported, more
and more countries and regions have put forward the climate goal of
“zero carbon” or “carbon neutrality” (Energy & Climate Intelligence
Unit).
How to achieve carbon neutrality has become an urgent issue to
solve for each country’s sustainable development. Developing
current carbon-intensive and low-efficiency energy system to future
deeply decarbonized, energy-efficient, and highly renewable solutions,
is one of the effective strategies to lower carbon dioxide emissions and
implement global carbon neutrality (Zhao and You, 2020).
Many traditional fossil fuel-based chemicals emit large amounts of
CO2 during production. Ethylene glycol (EG) is one such chemical,
which is widely used in the production of polyester, surfactant, anti-
freezing and solvent (Ding et al., 2017). With the rapid growth of
global polyester consumption, the ethylene glycol industry’s develop­
ment is attracting increasing attention. In 2003, its global production
capacity was about 16.51 million tons. In 2019, it significantly increased
to 36.69 million tons. Moreover, it is expected that the production ca­
pacity will continue to rise in the next few years and reach 60 million
tons by 2025 (Zhao et al., 2020). In general, there are three typical EG
production routes: oil-, coal- and biomass-based EG processes. However,
considering the entire life cycle of these three processes and ignoring
absorbed CO2 during plant growth; however, the global warming

* Corresponding author. School of Chemistry and Chemical Engineering, Hefei University of Technology, PR China.
E-mail address: ceqcyang@hfut.edu.cn (Q. Yang).

https://doi.org/10.1016/j.jclepro.2023.136540
Received 30 November 2022; Received in revised form 9 January 2023; Accepted 19 February 2023
Available online 20 February 2023
0959-6526/© 2023 Elsevier Ltd. All rights reserved.
Q. Yang et al.
potential of coal, oil and biomass-based ethylene glycol processes is
7.29 t-CO2-eq/t-EG, 4.52 t-CO2-eq/t-EG, and 3.84 t-CO2-eq/t-EG, respec­
tively (Xu et al., 2021). Therefore, although the life cycle CO2 emissions
of the BtEG process are lower than the other two processes, such a high
greenhouse emission undoubtedly contradicts the carbon-neutral
development goal advocated by the world.
Process integration and design optimization is an effective tool to
alleviate the serious carbon emission problem of conventional ethylene
glycol production routes (Manan et al., 2017). For example, Katebah
et al. (2022) carried out a process-level understanding of the
techno-economic advantages of process integration for CO2 reduction.
Chen et al. (2020) and Yang et al. (2021a) proposed that the ethylene
glycol production process can be coupled with the production process of
other chemicals, such as methanol and polymethoxy dimethyl ethers.
This method can indeed decrease CO2 emission and improve system
performance. However, increasing the hydrogen-to-carbon ratio of
syngas requires sacrificing a large amount of valuable CO gases, which
are converted into CO2. It then reuses CO2, which does not realize
endogenous carbon emission reduction (Hao et al., 2021). Integrating
hydrogen-rich resources can avoid the water gas shift unit to realize
low-carbon emissions and energy savings of the traditional fossil
fuel-based ethylene glycol processes (Sajjadi et al., 2021). For example,
Xiang et al. (2015) carried out a comparative work of coke oven gas and
natural gas-assisted coal to olefins processes with the conventional one
and found that these two assisted processes can greatly reduce carbon
emissions and improve energy efficiency. In addition, previous works
indicate that coke oven gas (2021a) and shale gas assisted (Yang et al.,
2021c) coal to ethylene glycol processes have lower carbon emission and
more satisfactory techno-economic performance.
However, the feasibility of these processes depends heavily on
whether there is an associated shale gas mine or coking plant in the area
where the ethylene glycol plant is located. Nevertheless, the resource
situation where most glycol plants are located differs from this situation.
Besides, so far, most of the proposed ethylene glycol production pro­
cesses are focused on improving the coal-based ethylene glycol process
and the increasement of hydrogen to carbon ratio by coke oven gas,
natural gas, or shale gas.
On the other hand, coal-based chemical processes integrated with
green hydrogen can significantly reduce CO2 emissions with high tech­
noeconomic performance. For example, Chirone et al. (2022) believed
that the green H2 from an alkaline electrolyzer is cheaper than that from
natural gas under the current natural gas, electricity prices, and carbon
Fig. 1. Overview of the differences between the conventional and proposed BtEG processes.
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Journal of Cleaner Production 396 (2023) 136540
tax. Do and Kim (2020) developed a renewable hydrogen assisted light
hydrocarbon production process and found that the proposed process
can achieve negative CO2 emission with high technoeconomic perfor­
mance. Zhou et al. (2022) proposed a novel coproduction process of
ammonia and fertilizer generation by integrating with the chemical
looping hydrogen technology. The results reveal that the proposed
process saves total production cost by 12.1% and reduces CO2 emissions
by 1.39 t/t. Moreover, Wang et al. (2022) proposed a coal to methanol
process integrated with green hydrogen. The results show that the direct
CO2 emission of the proposed process is reduced from 1.9 t/t to 0.04 t/t.
However, few studies investigate the integration of renewable resources
for ethylene glycol production. In addition, gasification agents signifi­
cantly affect syngas compositions and system performance. Previous
works have reported O2 (Liu et al., 2018), steam (Siwal et al., 2020), and
CO2 (Butterman and Castaldi, 2009). However, few studies consider the
impacts of gasification agents on the biomass to ethylene glycol process.
Herein, this work is mainly devoted to finding the optimal green
ethylene glycol production process from renewable resources with high
exergy efficiency, economic benefits, and environmental performance,
as shown in Fig. 1. Biomass is selected for ethylene glycol production by
integrating with biomass gasification technology because biomass is
renewable, easily available and carbon neutral. Renewable electricity
from wind and solar energy is applied to produce hydrogen by electro­
lyzing water technology to solve the element attribute of hydrogen
deficiency in biomass syngas. The discharged CO2 from the biomass
gasification is captured and reused to produce the target product (i.e.,
ethylene glycol) and co-produce dimethyl carbonate simultaneously.
This study addresses four critical gaps in current knowledge: (1) four
biomass to ethylene glycol (BtEG) processes integrated with different
gasification agents, green hydrogen production and CO2 utilization
technologies are designed and modeled; (2) the key operational pa­
rameters of these processes are explored and optimized along with the
validated models; (3) the effect of different gasification agents on the
biomass gasification unit is investigated and compared to select the most
suitable gasification agent; and (4) the technical, economic, and envi­
ronmental performance of four novel processes are compared with those
of the conventional process to manifest their advantages and disad­
vantages. The results of this study can provide the theoretical basis for
the industrialization of green ethylene glycol production from renew­
able resources.
Q. Yang et al.
2. Methodology
2.1. Process design and simulation
Chemical scientific experiments are aimed to explore promising
chemical synthesis conditions and mechanisms as well as new synthetic
pathways. For example, gasification is selected as the conversion tech­
nology of biomass because it is regarded as a preferable technology in
current and future low-carbon energy systems (He et al., 2021). It has
the following advantages: higher efficiency, fewer harmful emissions,
and cleaner syngas production (Habibollahzade et al., 2021). Although
biomass using air as a gasification agent is the simplest technology, the
dilution of N2 from air reduces the concentration of effective compo­
nents in syngas and hinders its application (Xiang et al., 2020). Thus,
oxygen as a gasification agent is more suitable for large-scale chemical
synthesis. Mixed CO2 as a gasification agent can potentially increase CO
content and carbon utilization efficiency (Wang et al., 2021), and mixed
with steam as a gasification agent could increase H2 content and
Fig. 2. Schematic block diagram of (a) conventional and (b) proposed BtEG processes.
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Journal of Cleaner Production 396 (2023) 136540
decrease CO2 content. Hence, biomass gasification using O2-only or
mixed with CO2 and steam could greatly affect syngas production.
However, limited literature has reported on the comparison among
different gasification agents.
In this study, four BtEG processes integrating with different gasifi­
cation agents are proposed as shown in Fig. 2(a) and (b) and Fig. S1,
including O2-only, O2+CO2, O2+steam, and O2+CO2+steam, respec­
tively. Herein, five processes are considered in this study.
Case 1: conventional BtEG process (O2-only as the gasification agent)
Case 2: proposed BtEG process with O2-only gasification agent
Case 3: proposed BtEG process with O2 and CO2 gasification agents
Case 4: proposed BtEG process with O2 and steam gasification agents
Case 5: proposed BtEG process with O2, CO2 and steam gasification
agents
Different from the conventional BtEG process, Cases 2–5 reduce two
units, i.e., air separation (ASU) and water gas shift (WGS) units, and
Q. Yang et al.
integrate two additional units: renewable electricity for hydrogen pro­
duction (REH) and carbon dioxide utilization (CDU) unit. Thanks to
Cases 2–5 integrating electrolyzed water to produce hydrogen with the
aid of renewable electricity, the syngas from the biomass gasification
(BG) unit will no longer need to undergo a water-gas shift. As a result, a
large amount of CO can be retained to synthesize ethylene glycol instead
of being wasted as CO2. Because biomass-based syngas contains a certain
amount of CO2, SO2 and other acid gases, it is firstly sent to the acid gas
removal (AGR) unit to remove these impurities. The purified syngas
enters the H2 and CO separation (HCS) unit to generate high-purity
hydrogen and CO streams, which are used to produce ethylene glycol
in the ethylene glycol synthesis (EGS) unit. The flow information of the
material and energy streams of the conventional and proposed BtEG
processes is required to be identify by establishing their whole process
modeling and simulation before determining their technical, economic
and environmental performance. The schematic flowsheet of Cases 2–5
is shown in Fig. 3.
To shorten the length of the paper, the whole schematic flowsheet of
the conventional BtEG process (Case 1) is present in Fig. S2, and the
description of the modeling and simulation of the acid gas removal, H2
and CO separation, and ethylene glycol synthesis units are detailed
explained in Appendix A.1-A.3 in the Supporting Information. Besides,
the key operational parameters of Cases 1–5 processes are summarized
in Table S1 Appendix B in the Supporting Information. The RK-SOAVE
Fig. 3. Schematic diagram of the whole flowsheet of Cases 2-5.
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Journal of Cleaner Production 396 (2023) 136540
method is selected as the global physical method because most of the
substances contained in the BtEG process are non-polar or weakly polar
substances. Since the substances processed by the EGS unit have more
polar substances, the physical property method of this unit is defined as
the NRTL method.
2.1.1. Biomass gasification unit
The simplified mechanism and modeling of the biomass gasification
unit are shown in Fig. 4 (a) and (b). The biomass gasification process
generally consists of drying, pyrolysis, gasification and combustion
stages (Xiang et al., 2020). Biomass is firstly got into the drying stage
(modeled by an RStoic model and a Sep model) to remove moisture and
dry biomass under 150 ◦ C. As the temperature rises, the dried biomass
goes into the pyrolysis stage, where the decomposition speed increases,
resulting in a large number of decomposition products, such as coke, tar,
CO2, CO, methane, etc. This stage is assumed to be modeled by an RYield
model (275 ◦ C) and an RStoic model (about 500 ◦ C). The separated coke
is fed into the gasification and combustion stage, which is modeled by an
RGibbs model and a Sep model. The gaseous streams of the three stages
are mixed as the crude syngas of the biomass gasification process. The
basic properties of the selected biomass are indicated in Table S2. In
addition, the chemical reaction and the key kinetic parameters for the
modeling and simulation of the biomass gasification unit are shown in
Tables S3 and S4 in the Supporting Information.
Q. Yang et al. Journal of Cleaner Production 396 (2023) 136540

Fig. 4. Simplified gasification mechanism (a) and modeling (b) of biomass gasification unit.

2.1.2. Renewable electricity for hydrogen production unit voltage is composed of open circuit voltage (Vocv), activation
Hydrogen production by electrolysis of water is a green and envi­ overpotential (Vact), diffusion overpotential (Vdiff), and ohmic
ronmentally friendly hydrogen production, which produces hydrogen overpotential (Vohm), which can be expressed as shown in Eq. (2):
by providing energy to water through electric energy and destroying the
Eele = Icell Acell Ncell V (1)
hydrogen-oxygen bonds of water molecules (Zhang et al., 2021a). There
are three typical hydrogen production technology by electrolysis of
Vcell = Vocv + Vact + Vdiff + Vohm (2)
water: alkaline water electrolysis (AWE), proton exchange membrane
electrolysis (PEM), and solid oxide electrolysis (SOEC), as shown in The open circuit voltage, which is also called reversible potential, is
Table S5. It shows that the alkaline water electrolysis hydrogen pro­ determined by the Nernst equation as follows (Falcão and Pinto, 2020):
duction technology has many disadvantages, such as strongly corrosive, ( )
RT αH2 α0.5
low energy conversion efficiency, low current density, and complex Vocv = V0 + ln
O2
(3)
zF αH2 O
product gas dealkalization. PEM technology overcomes the drawbacks
of alkaline water electrolysis technology, and separates the produced
where R and F are the gas and Faraday constant, T refers the electrolysis
hydrogen and oxygen gases without additional separation procedures.
temperature, z is the number of moles of electrons involved in the
As a result, it has the promising merits of high electrolysis efficiency, no
electrolysis reaction, αi is the activity of substance i, V0 is the open cir­
pollution, high current density, small size, and can change the load
cuit voltage at standard temperature and pressure, which is estimated as
quickly. In addition, PEM technology can well match the features of the
(Toghyani et al.):
photovoltaic and wind power technology. For example, it can match the
( )
randomness and fluctuation of these power generation. Due to the solid αH2 α0.5
(4)
O2
V0 = 1.23 − 0.0085(T − 298) + 4.38 × 10− 5 T ln
oxide electrolytic cell has not been commercialized, PEM technology is α H2 O
used to produce hydrogen in this work. Its simplified mechanism and
modeling procedures are shown in Fig. 5 (a) and (b). The electrolytic activation overpotential is due to the loss during the
electrochemical activation process, which is affected by many factors,
(1) Electrochemical model: The electricity consumption of the PEM such as temperature, catalyst performance, and electrode morphology.
electrolyzer can be expressed by the relationship between cell The Butler-Volmer equation describes the basic electrochemical rela­
voltage (Vcell) and current (Icell) as shown in Eq. (1). The cell tionship between current and activation overpotential in the electro­
chemical dynamic process:

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Q. Yang et al. Journal of Cleaner Production 396 (2023) 136540

Fig. 5. Electrochemical model (a) and flowsheet-based model of the REH unit.

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Q. Yang et al. Journal of Cleaner Production 396 (2023) 136540

Vact = Vact,a + Vact,c (5) Dehydrating reaction: EO + H2O → EG (11)

⎛
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ ⎞
( ) √ ( )2
RTa j RTa ⎜ j √ j Overall reaction: CO2 + 2 CH3OH + EO → DMC + EG (12)
⎟
Vact,a = sinh− 1 = ln⎝ + √1 + ⎠ (6)
αa F 2jo,a αa F 2jo,a 2jo,a The conversion ratio yield of the CO2 conversion reaction, however,
is much less than 10% because of thermodynamic stability of carbon
( )
⎛ √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
√ ( )2
⎞ dioxide (Gu et al., 2021) as shown in Fig. 6(a). Thus, to increase the
RTc j RTc ⎜ j √ j ⎟ conversion of this reaction from around 10% in a one-step reactor to
Vact,c = sinh− 1
= ln⎝ + √1 + ⎠ (7)
αc F 2jo,c αc F 2jo,c 2jo,c 99.5%, an in-situ hydration-assisted reactive distillation column with a
side reactor is employed in this study as indicated in Fig. 6(b) (Hu et al.,
2018). In this regard, the flowsheet of the CDU unit is developed as
where j is current density, and subscript a and c stand for the anode and
shown in Fig. 6(c). Fresh methanol is mixed with recycled CO2 and then
cathode.
enters the reactive distillation column (RadFrac model), where contact
The diffusion overpotential is caused by the hindered transfer of
with methanol enter the top of the column. The CH3OH and CO2 in the
reactants and products in the porous electrodes in the PEM electrolyzer,
gas phase enters the side reactor, which is modeled by a REquil model
which can be formulated as follows:
and RPlug model. The REquil model is used to simulate the CO2 con­
( ) ( )
RTa CO2 ,m RTa CH2 ,m version (Eq. (13)) with a reaction equilibrium model as shown in Eq.
Vdiff = Vdiff,a + Vdiff,c = ln + ln (8)
4F CO2 ,m0 2F CH2 ,m0 (13) (Wu and Chien, 2019). The RPlug model is adopted to simulate the
dehydrating reaction (Eq. (14)) with a kinetics model as shown in Eq.
where CO2 ,m and CH2 ,m denote the oxygen and hydrogen concentrations (14) (Wu and Chien, 2019). The output of the side reactor is compressed
at the interface between the membrane and the porous electrode, which and recycled into the reactive distillation column. The bottom stream of
can be calculated by Fick’s law. this column, which mainly consists of EG and DMC, can easily separate
The ohmic overpotential is mainly caused by the resistances of the in the distillation column due to the high relative volatility between EG
bipolar plate, electrode, and membrane between different layers. It is and DMC (Zheng et al., 2021).
greatly related to the electrode material and type of PEM. It has a linear /
ln Keq = − 201.9 + 43088 T + 0.22T (13)
relation with the current density as follows (Falcão and Pinto, 2020):
( ) ( )
Vohm = Rpl + Rel + Rmem j (9) r mol ⋅ s− 1 ⋅ cm− 3 = 3.15 × 109 exp(− 9547 / T)xEO xH2 O (14)

where Rpl, Rel and Rmem are bipolar plate, electrode, and membrane
resistances.
The detailed physical properties and operating parameters for the
REH unit simulation are presented in Table S6 in the Supporting
Information.
where Keq is the reaction equilibrium constant, r is reaction rate, and xi is
the conversion ratio of ith substance, respectively.
2.2. Efficiency analysis method

(2) Flowsheet-based model: Fresh water is mixed with recycled Element utilization efficiency is able to effectively distinguish the
water and then enters the purification unit (Sep model), where resource conversion and utilization efficiency of the traditional and
only 50% of the flow can be used for the subsequent electrolysis proposed processes because these processes involve material conver­
process (Rivera-Tinoco et al., 2016). Purified water is fed into the sion. Due to the purpose of the proposed processes is aimed to use carbon
stacks. An RStoic model is used for the simulation of the elec­ to reduce carbon emissions effectively. Therefore, the carbon utilization
trochemical reaction. The following splitters (FSplit models), efficiency (εC) is used in this study. It is the ratio between the output and
mixers (Mixer models) and separators (Sep models) of the stack input carbon of the system as formulated as follows (Yang et al., 2021d):
are used to simulate gas permeability and water-drag through the C
Foutput C
FEG C
+ FDMC
membrane, as well as unreacted water evacuation under the εC = × 100% = C × 100% (15)
C C C
conditions of adiabatic without pressure loss. (Rivera-Tinoco Finput Fbiomass + Fmethanol + FEO
et al., 2016). The Flash2, Heater, and Sep models are used to
C C
simulate the hydrogen purification, drying and pressurization where Finput and Foutput are the mole flowrate of input and output carbon;
C C C C C
processes. The oxygen-water mixture stream is fed into the flash Fbiomass , Fmethanol , FEG , FEO and FDMC denote the mole flowrate of biomass,
tanks and heater to separate oxygen and water. The obtained methanol, EG, EO and DMC, respectively.
hydrogen stream will be used to synthesize ethylene glycol in the Because the carbon utilization efficiency fails to reflect the efficiency
following unit. The oxygen stream is divided into two parts: one is of the system’s energy conversion intuitively, the exergy analysis
fed into the biomass gasifier as a gasification agent; the rest is sent method is a such method that can not only determine the magnitude of
to the methyl nitrite synthesis reactor for methyl nitrite energy loss, but also distinguish the difference in energy quality. Hence,
production. this method is adopted to analyze the thermodynamic performance of
different BtEG processes.
2.1.3. CO2 utilization unit The exergy of a stream (Ex) mainly involves the physical exergy
The direct synthesis of dimethyl carbonate (DMC) from CO2 and (Exph) and chemical exergy (Exch) as follows (Wu et al., 2021):
methanol is adopted as the CO2 utilization technology in this work.
Ex = Exph + Exch (16)
Firstly, it is a green synthetic route due to the nontoxicity of starting
materials and synthetic process, as shown in Eq. (10) (Zhang et al., ∑
Exph = ni ((hi − h0 ) − T0 (si − s0 )) (17)
2021b). Secondly, DMC plays a significant role in the chemical industry i
because it is widely used as a fuel additive, green organic synthesis in­
( )
termediate, and solvent. Thirdly, introducing ethylene oxide (EO) as the ∑ni ch,o ∑ni (ni )
dehydrating agent of this technology is able to byproduce the target Exch = n ex + RT ln (18)
n i n n
products in the same amount as DMC as shown in Eqs. (11) and (12). i i

CO2 conversion reaction: CO2 + 2 CH3OH → DMC + H2O (10) where h and s are the molar enthalpy and entropy, exch,o
i is the standard

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Q. Yang et al. Journal of Cleaner Production 396 (2023) 136540

Fig. 6. Mechanism (a), conceptual design (b) and simulation model (c) of the CDU unit.

chemical exergy of ith species, and n is the mole flowrate. Information.

Exergy efficiency (φ), one of the most efficient evaluation metrics of ( )n
Q
exergy method, is defined as the ratio of the output and input exergy as EI = EIref × (20)
Qref
follows (Wu et al., 2021):
( ∑ )
Exoutput ExEG + ExDMC
φ= × 100% = × 100% (19) TCI = EI 1 + RFi (21)
Exinput Exraw + Exsteam + Exelectricity

where Exinput and Exoutput are the input and output exergy; Exraw , Exsteam
and Exelectricity represent the input exergy of raw material, steam and
electricity, respectively; ExEG and ExDMC are the product exergy of EG
and DMC.
2.3. Economic analysis methodology
The estimation of total capital investment (TCI) and total production
cost (TPC) is an important reference basis for analyzing the economic
prospect of the proposed process. Although the processing scale of the
same unit is different, the total capital investment of the same unit can
be estimated by the Equipment Capacity Index method. This method is a
common method to estimate the investment of a new project based on
the processing scale of the new project as well as the processing scale
and total capital investment of the successfully operated plant as shown
in Eqs. (20) and (21) (Shi et al., 2021). The benchmark case for the
calculation of equipment investments is summarized in Table S7. When
the equipment cost is determined, the rest costs of TCI are estimated in
terms of their ratio factor (RF) as shown in Table S8 in the Supporting
where EI and Q stand for the equipment investment and processing scale
of the estimated project, EIref and Qref refer to the equipment investment
and processing scale of the successfully operated plant, and n is the
scaling exponent, respectively.
The TPC of the conventional and proposed BtEG processes are the
sum of manufacturing cost (CM) and general expense (CGE) as shown in
Eq. (22) (Yang et al., 2021b). The manufacturing cost includes raw
material, utility, operating and maintenance, depreciation and plant
overhead costs as shown in Eq. (23) (Das et al., 2021). The CGE mainly
includes management, financial and sales expenses as shown in Eq. (24).
TPC = CM + CGE (22)
CM = CR + CU + CW + COM + CD (23)
CGE = CME + CFE + CSE (24)
where CR and CU are the cost of raw material and utilities; CW denotes
the wage, including additional fees such as wages, allowances and bo­
nuses for production personnel; COM is other operating and maintenance

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Q. Yang et al. Journal of Cleaner Production 396 (2023) 136540

cost; and CD is the depreciation cost, which is estimated by the These gas emissions come from two sources: one is the direct GHG
assumption of the salvage value and plant lifetime are 5% and 20 years. emissions from the production process, and the other is the indirect GHG
To further analyze the profitability of the proposed processes, the net emissions from the use of energy and raw materials (Xu et al., 2021). The
present value (NPV) and internal rate of return (IRR) are adopted in this direct GHG emissions can be analyzed in terms of the modeling and
work as shown in Eqs. 25 and 26 (Lee et al., 2021). In this work, the simulation results, and the indirect GHG can be calculated by Eq. (27)
plant lifetime and discount rate (i0) are assumed to be 20 years and 10%. (Qiu et al., 2010). When the CO2, N2O, and CH4 in each stage are
The construction period of the project is two years, and the cost of the determined, the total GHG emissions of the conventional and proposed
first year accounts for 80% of the total investment cost (Yang et al., BtEG processes can be calculated by Eq. (28) (Davidson et al., 2021).
2022). ∑∑
GHGk = ECi,j ×GHGFi,j,k (27)
∑s
NCFt i k
NPV = t (25)
t=0 (1 + i0 ) ∑ ∑ ∑
GHG = 298 × N2 O + 25 × CH4 + CO2 (28)
i i i
∑
s
NCFt
NPV = =0 (26)
t=0 (1 + IRR)t Where ECi,j denotes the consumption of energy j in the ith stage; and
GHGFi,j,k refers to the factor of kth pollutant emission (k ∈ {CO2, N2O,
where NCFt denotes the annual undiscounted net cash flow in year t. and CH4 }) in ith stage because of the consumption of energy j, which
can be found in the previous work of Xu et al. (2021).
2.4. Environmental assessment methodology
3. Results and discussion
Life cycle assessment (LCA) is used to evaluate the environmental
3.1. Optimization of key operational parameters
impact based on the boundary of “cradle to gate” in this work. The
detailed system boundary of the study consists of raw material acqui­
The feed ratio among input O2, CO2, steam and biomass of the four
sition, transportation and production stages as shown in Fig. 7. The data
proposed processes is investigated and optimized to have a better system
of the biomass acquisition and transportation stages mainly select from
performance in terms of the established models in section 2.1. In addi­
research papers on similar topics (Shafie et al., 2014; Singh & Basa k,
tion, the reaction pressure of the side reactor as well as the feed stage of
2019), and the data of the ethylene glycol production stage is calculated
CO2, methanol, and recycle streams of the reaction distillation column of
on the basis of the simulation results. This study selects one ton of
the proposed BtEG processes are investigated to utilize the CO2 gener­
ethylene glycol product as the functional unit. Because four proposed
ated by the conventional BtEG process efficiently.
BtEG processes are aimed to optimize the material-energy utilization
structure of the conventional process to achieve green and carbon
3.1.1. Effect of CO2/biomass and O2/biomass ratios on the syngas
neutrality of the ethylene glycol production, this work is focused on the
Properly increasing the feed ratio of CO2 can effectively reduce CO2
evaluation of the greenhouse gas (GHG) emissions of the conventional
emissions, but it will undoubtedly have a greater impact on the syngas
and proposed BtEG processes to manifest the CO2 reduction ability of the
produced by biomass gasification units (Habibollahzade et al., 2021).
process (Yan et al., 2021). According to the production characteristics of
The effect of the CO2/biomass and O2/biomass on the syngas is indicated
the BtEG process, GHG emissions mainly consider CO2, N2O, and CH4.

Fig. 7. System boundary of the different BtEG processes.

9
Q. Yang et al.
Fig. 8. Effect of CO2/biomass and O2/biomass ratios on the total amount and ratio of H2 and CO.
Fig. 8(a) and (b). Increasing the ratio of CO2/biomass has less impact on
the total amount of CO and H2 in the syngas, but has a significant impact
on the H2/CO ratio of the syngas. It means that increasing CO2/biomass
ratio can increase the production of CO but decrease that of H2. It is
mainly because that increasing the amount of CO2 promotes the reaction
of carbon and CO2 to produce CO, but inhibits the WGS reaction. Hence,
the syngas will have a lower H2/CO ratio. The O2/biomass ratio greatly
impacts on the total amount of CO and H2 as well as the H2/CO ratio.
The total amount of CO and H2 are increased quickly when the
O2/biomass ratio increases from 0.1 t/t to 0.2 t/t. But it is then
decreased when the O2/biomass ratio is higher than 0.2 t/t. This is
mainly due to properly increasing the oxygen content can provide more
heat to promote the gasification reaction, but excessive oxygen will
rapidly increase the combustion reaction of CO and H2. Thus, the
optimal O2/biomass ratio is 0.2 t/t to increase the yield of effective
components in the syngas. In addition, to consume as much CO2 as
possible and have a not too low H2/CO ratio, the CO2/biomass ratio of
the proposed Cases 3 and 5 is suggested to be 0.2 t/t.
Fig. 9. Effect of steam/biomass and O2/biomass ratios on the total amount and ratio of H2 and CO.
10
Journal of Cleaner Production 396 (2023) 136540
3.1.2. Effect of steam/biomass and O2/biomass ratios on the syngas
Unlike the CO2 agent, using steam as a gasification agent can effec­
tively increase hydrogen production in the syngas as shown in Fig. 9(a)
and (b). Due to the molar ratio of the consumed CO and produced H2 of
the water gas shift reaction to 1:1, the total amount of H2 and CO is
almost unchanged if the O2/biomass ratio does not change as shown in
Fig. 9(a). When the steam/biomass ratio adds from zero to 0.5 t/t, the
H2/CO ratio is increased from 0.7 to higher than 1.1. It is mainly because
that a high steam/biomass ratio can promote water gas shift and
methane reforming reactions, resulting in a significant increase in the
output H2 as shown in Fig. 9(b). Moreover, the O2/biomass ratio has a
more significant effect on the total amount and ratio of H2 and CO
compared with that of steam/biomass ratio. In particular, the total
amount of H2 and CO is firstly increased and then decreased when the
O2/biomass ratio is increased from 0.1 t/t to 0.3 t/t. When the O2/
biomass ratio is high to 0.2 t/t, the biomass gasification unit has the
highest amount of H2 and CO. Thus, the O2/biomass ratio and the
steam/biomass ratio of the proposed Case 4 and Case 5 are
Q. Yang et al.
recommended to be 0.2 t/t and 0.2 t/t.
3.1.3. Effect of CO2/biomass and steam/biomass ratios on the syngas
When the O2/biomass ratio is 0.2 t/t, the effect of CO2/biomass and
steam/biomass ratios on the syngas is indicated in Fig. 10 (a) and (b).
When the CO2/biomass and steam/biomass ratios are changed from zero
to 0.5 t/t, the change ratio of the total amount of H2 and CO is less than
2.5% as shown in Fig. 10(a). However, the H2/CO ratio of the syngas is
changed from 0.86 to 1.41 when the steam/biomass ratio increases from
zero to 0.5 t/t, and it is changed to 0.60 when the CO2/biomass ratio is
higher to 0.5 t/t. Hence, to consume as much CO2 as possible and have a
not too low H2/CO ratio, the O2/biomass, CO2/biomass and steam/
biomass ratios of Case 5 are all suggested to be 0.2 t/t in this study.
3.1.4. Effect of pressure on the conversion of side reactor and RD process
Due to the synthesis of dimethyl carbonate from CO2 and methanol is
a chemical reaction involving gas, the performance of the side reactor
and reaction distillation process will be greatly influenced by the reac­
tion pressure as shown in Fig. 11 (a) and (b). If the reactants are fed
according to the stoichiometric coefficient, the temperature is increased
from 110 ◦ C to 131 ◦ C when the pressure increases from 0.75 MPa to
1.50 MPa. As a result, the equilibrium conversion of the side reactor is
decreased from 12.21% to 10.01%. It is mainly because that the
dimethyl carbonate synthesis reaction is an exothermic reaction.
Increasing temperature chemical equilibrium proceeds in the opposite
direction according to the principle of chemical equilibrium. The low
equilibrium conversion has a negative impact on the reaction distillation
process; however, appropriately increasing pressure has a positive
impact on the separation efficiency of the distillation process. Hence,
determining pressure requires weighing its impact on the reaction and
reactive distillation process. As Fig. 11(b) shows, when the pressure is
increased from 0.75 MPa to 1.0 MPa, the methanol conversion and mole
fraction of DMC in the bottom of the column are greatly decreased, but
they are significantly increased if the pressure is higher than 1.0 MPa. It
is because that the effect of the pressure on distillation will become
stronger and stronger and weaken its impact on the reaction simulta­
neously along with the increase of the pressure.
3.1.5. Effect of feed stage on the methanol conversion ratio of the CDU unit
The feed stage of the recycle, methanol, CO2 and EO streams of the
column greatly affects the methanol conversion ratio as shown in
Fig. 10. Effect of CO2/biomass and steam/biomass ratios on the total amount and ratio of H2 and CO.
11
Journal of Cleaner Production 396 (2023) 136540
Fig. 12. When the feed stage of the recycle stream is set in the upper sixth
stage, the methanol conversion ratio is gradually raised from 93.0% to
99.3%, thanks to the reuse of the unconverted reactants. That ratio,
however, is slightly decreased if the stage of the recycle stream is set
below the sixth stage. It is mainly because that a small amount of the
unreacted substances will reach the side withdrawal stage. Therefore,
the recycle stage of the RD column is set to 6.
Due to the methanol conversion ratio of the column is decreased
when the stage of the methanol stream is at the lower stage. Hence, the
first stage is selected as the feed stage of the methanol stream. Moreover,
the feed stage of the CO2 stream has less impact on the conversion ratio
of methanol compared with other feed streams. It has only an obvious
downward trend when the feed stage of the CO2 stream is changed from
5 to 6. Thus, the feed stage of the CO2 stream is selected to be 5.
The EO stream is employed as the dehydrant. Selecting a reasonable
feed stage will significantly increase the conversion ratio of methanol. It
can be seen that the feed stage of the EO stream changes from 3 to 4, and
the methanol conversion ratio rises from 99.0% to 99.6% because EO
reacts with the produced water can promote the CO2 to DMC reaction.
However, when the feed stage of the EO stream varies from 4 to 10, the
methanol conversion ratio greatly drops from 99.6% to 85.2%. Thus, the
feed stage of the EO stream is suggested to be 4.
3.2. Comparison of different gasification agents on the BG unit
The difference in gasification agent has the most direct impact on the
biomass gasification unit in comparison with other units. As aforemen­
tioned, Cases 1 and 2 use oxygen as the gasification agent, Case 3 uses O2
and CO2, Case 4 uses O2 and steam, and Case 5 uses a mixed gasification
agent of O2, CO2 and steam. The effect of the gasification agents on the
performance of the biomass gasification unit of these processes is shown
in Fig. 13. Compared with a process that uses only oxygen as the gasi­
fication agent (Cases 1 and 2), Cases 3–5 using a mixed gasification
agent will have higher syngas production, especially Case 5. This is
mainly caused by the synergistic effect between different gasification
agents. Specifically, Case 3 has the highest yield of CO due to the CO2
being reacted with carbon and converted to CO; Case 4 has the highest
yield of H2 because of the water gas shift and methane steam reforming
reactions. Therefore, O2 mixing a certain amount of CO2 and steam is
beneficial to produce more syngas, save raw materials and improve
resource utilization efficiency.
Q. Yang et al.
Fig. 11. Effect of pressure on the reaction and reaction distillation process.
Fig. 12. Effect of feed stage on the methanol conversion of the CDU unit.
3.3. Technical performance assessment
To compare the system performance of the conventional process
(Case1) and the four novel processes (Cases 2–5), their production scales
are the same to 4 × 105 t/y (i.e., 50 t/h), which refers to a practical 4 ×
105 t/y ethylene glycol project invested by National Energy Group Yulin
Chemical Co., Ltd., located in Yulin, Shaanxi Province, China. The key
simulation results of Cases 1–5 are calculated and shown in Table 1. It
should be noted that the detailed simulation results of the conventional
and proposed BtEG processes, which involve material and energy bal­
ance as well as molar fraction of the main streams, can be found in
Tables S9 and S10 in the Supporting Information.
3.3.1. Comparison of carbon utilization efficiency
The carbon flow of Cases 1–5 is determined with the aid of the
established models in section 2.1, as shown in Figs. S5(a)–(e). The input
carbon of the biomass gasification unit of Cases 2–5 is reduced from
4104 kmol/h to 2035 kmol/h, 1987 kmol/h, 1856 kmol/h, and 1998
kmol/h, respectively. It is because that lots of CO in Case 1 is converted
to CO2 to increase the amount of hydrogen in the water gas shift unit.
12
Journal of Cleaner Production 396 (2023) 136540
Fig. 13. Effect of different gasification agents on the performance of the
biomass gasification unit.
But the generated CO2 cannot be consumed in this process. Cases 2–5
integrate renewable electricity for the H2 production unit to make up for
the insufficient hydrogen, so the water gas shift unit is no longer
required. In addition, the O2 mixing of a certain amount of CO2 and
steam can increases the production of syngas, and integrating CO2 uti­
lization unit can reuse the emitted CO2 and improve the carbon utili­
zation efficiency of the conventional process. In this regard, the CO2
utilization unit of Cases 2–5 reuses 148 kmol/h, 102 kmol/h, 260 kmol/
h, and 176 kmol/h, respectively. As a result, these reused CO2 are
reacted with the methanol and ethylene oxide to produce 142 kmol/h,
101 kmol/h, 259 kmol/h, and 175 kmol/h EG in Cases 2–5, respectively.
Moreover, the by-product (DMC) of the CO2 utilization unit of Cases 2–5
contains 425 kmol/h, 304 kmol/h, 776 kmol/h, and 525 kmol/h,
respectively.
The distributions of the total input and output carbon of Cases 1–5
are determined according to their carbon flow results as shown in
Fig. 14. In addition to Case 1, the input carbon of Cases 2–5 contains
biomass, ethylene oxide and methanol for the reuse of CO2. Thanks to
the green hydrogen and CO2 utilization technologies, the total input
carbon of Cases 2–5 is decreased by 36.54%, 41.89%, 29.44%, and
Q. Yang et al. Journal of Cleaner Production 396 (2023) 136540

Table 1 methanol and ethylene oxide for CO2 reuse. The exergy input for this
Key simulation results of Cases 1-5. part of Cases 2–5 is about 107.75 MW, 76.90 MW, 196.68 MW, and
Case 1 Case 2 Case 3 Case 4 Case 5 132.92 MW, respectively. In addition, Case 2–5 require more electricity
for the green hydrogen production in the REH unit by 140.54 MW,
Input biomass (t/h) 105.24 52.17 50.72 47.58 51.23
Consumed CO2 (kmol/ 0.00 141.79 101.20 258.82 174.92 200.82 MW, 108.89 MW, and 148.59 MW, respectively. Thus, the total
h) exergy input of Cases 2–5 is increased from 522.51 MW to 558.15 MW,
H2 from BG unit (kmol/ 3465.00 1467.02 1024.54 1225.19 1223.88 579.42 MW, 610.83 MW, and 599.46 MW, respectively. But Cases 2–5
h) integrating with the CDU unit can by-produce DMC, 48.39 MW, 34.53
H2 from REH unit 0.00 1388.77 2005.65 1127.76 1489.56
(kmol/h)
MW, 88.32 MW, and 59.69 MW, respectively. Thus, the exergy effi­
Total input H2 (kmol/ 3465.00 2855.79 3030.19 2352.95 2713.45 ciency of Cases 2–5 is increased from 50.75% to 56.18%, 51.73%,
h) 57.88%, and 54.20%, respectively, as shown in Fig. 15(a). As Fig. 15(b)–
Input O2 of BG unit (t/ 21.05 10.43 10.14 9.52 10.25 (e) shows, the exergy destruction of the EGS unit of Cases 2–5 is the
h)
largest, followed by the BG and REH units. The main reason is that the
Input steam of BG unit 0.00 0.00 0.00 9.52 10.25
(t/h) flowsheet of the EGS unit is the most complicated, including DMO
Input methanol of CDU 0.00 286.41 204.42 522.82 353.33 synthesis and separation as well as EG synthesis and refinery sections.
unit (kmol/h) Irreversibility of the reaction and separation of DMO and EG makes the
Input EO of CDU unit 0.00 141.79 101.20 258.82 174.92 EGS unit have large exergy destruction. Since the BG unit reacts at high
(kmol/h)
EG from EGS unit (t/h) 50.00 41.21 43.73 33.95 39.16
temperatures, it increases the exergy destruction of the process. As the
EG from CDU unit (t/h) 0.00 8.79 6.27 16.05 10.84 PEM water electrolysis hydrogen production technology still has high
By-produced DMC (t/ 0.00 12.90 9.21 23.55 15.92 power consumption, the REH unit also has relatively large exergy
h) destruction. Therefore, to improve the technical performance of the
proposed BtEG processes, it priorities improving the exergy efficiency of
EGS, BG, and REH units.
34.19%, respectively. The ratio of carbon introduced by biomass to the
In summary, from the perspective of carbon utilization efficiency and
total carbon input of Case 2–5 is dropped from 100% to 78.12%,
exergy efficiency, Case 4 has the best technical performance, followed
82.94%, 64.07% and 73.97%, respectively. By integrating efficient CO2
by other proposed processes and the conventional process (Case 1).
reuse technology, Cases 2–5 can produce as much EG as Case 1, and can
also produce more by-products of 141.79 kmol/h, 101.20 kmol/h,
258.82 kmol/h, and 174.92 kmol/h DMC, respectively. The by-product
DMC of Cases 2–5 can increase carbon output by an additional 20.87%,
15.84%, 32.50%, and 24.55%, respectively. As a result, the carbon
utilization efficiency of Cases 2–5 is increased from 39.30% to 78.26%,
Table 2
80.36%, 82.50%, and 79.14%, respectively. Therefore, Case 4 has the
Comparison of the exergy input and output of the proposed BtEG processes.
highest resource utilization efficiency, followed by Case 3 and Case 5.
Case 1 Case 2 Case 3 Case 4 Case 5

3.3.2. Comparison of exergy efficiency Biomass 462.32 239.11 232.47 218.08 234.80
When clarifying the material conversion of the conventional and Methanol 56.98 40.67 104.01 70.29
Ethylene oxide 50.77 36.23 92.67 62.63
proposed processes, an exergy analysis of Cases 1–5 is conducted and
Electricity 38.95 179.49 239.77 147.84 187.54
indicated in Table 2. The total exergy input of biomass of Cases 2–5 is Steam 21.24 31.80 30.28 48.23 44.20
significantly decreased by 48.28%, 49.72%, 52.83%, and 49.21%, Total input 522.51 558.15 579.42 610.83 599.46
respectively. The main reason is that the carbon utilization efficiency of Ethylene glycol 265.20 265.20 265.20 265.20 265.20
Dimethyl carbonate 48.39 34.53 88.32 59.69
Cases 2–5 is much higher than that of Case 1, which greatly reduces the
Total output 265.20 313.58 299.73 353.52 324.89
consumption of raw biomass. However, Case 2–5 require additional

Fig. 14. Distributions of the total input and output carbon of different BtEG processes.

13
Q. Yang et al.
Fig. 15. Exergy efficiency (a) and distributions of the exergy destruction (b–e) of the proposed BtEG processes.
3.4. Economic performance assessment
3.4.1. Comparison of total capital investment
The TCI and its distributions of the conventional and proposed BtEG
processes are estimated based on the economic models established in
section 2.3 as shown in Fig. 16. The TCI of Case 4 is the lowest, 588.33 M
$, followed by Case 2, 607.98 M$, and Case 5, 612.50 M$ as shown in
Fig. 16 (a). That of the conventional BtEG process (Case 1) is the highest,
747.70 M$. The proposed processes (Cases 2–5) have relatively low total
capital investment because that (1) the processing scale of the BG unit of
these processes is lower than the conventional process by 48.28%,
49.72%, 52.83%, and 49.21%, respectively; (2) the WGS and ASU units
of Cases 2–5 are removed for their insufficient hydrogen is provided by
the REH unit; (3) the investment cost of the AGR and HCS unit is greatly
decreased because their input streams are obviously decreased; and (4)
the investment cost of the EGS unit is significantly decreased for part of
the EG product is produced by the CDU unit with CO2 reuse.
According to the breakdown cost analysis results (shown in Fig. 16
(b) and (d)), the investment cost of the EGS unit accounts for the largest
proportion of the TCI of both the conventional and proposed BtEG
processes, which is in range of 53%–58%; followed by the AGR unit,
15%–19%, and the BG unit, 11–14%. However, there is an obvious
difference in the distribution of the equipment costs of the three units.
For example, the reactor, column and heat exchanger of the EGS unit
accounts for the largest proportion of its total equipment cost, ac­
counting for 45%, 25% and 15%, respectively. But that of the AGR unit
is column, flash and heat exchanger, accounting for 53%, 30% and 15%,
respectively.
14
Journal of Cleaner Production 396 (2023) 136540
More specifically, the total costs of the reactor, column and heat
exchanger account for the largest proportion of the equipment cost of
the conventional and proposed BtEG processes as indicated in Fig. 16(c)
and (e). Their proportions are in the range of 35%–36%, 28%–29%, and
15%–17%, respectively. Different from the conventional BtEG process,
Cases 2–5 have no equipment cost for ASU and WGS units, but add the
equipment cost of REH and CDU units. Thus, with the avoidance or
significant reduction of investment cost in complex units, Cases 2–5,
despite the addition of two new units, still have a lower total investment
cost than the conventional process, especially Case 4.
3.4.2. Comparison of total production cost
The raw material and utility costs are the two most important com­
ponents of the total production cost of a chemical process. These two
costs of Cases 1–5 are calculated in terms of the unit price and annual
consumption of their raw material and utility as shown in Table 3.
Moreover, the rest costs of the total production cost of conventional and
proposed BtEG processes is calculated according to the assumption in
Table S11. As Fig. 17 shows, Case 4 has the highest total production cost,
379.19 M$/y, followed by Case 5, 340.57 M$/y, and Case 3, 309.48 M
$/y. The conventional process has the lowest total production cost. The
main reasons are that Cases 2–5 need to consume a certain amount of
ethylene oxide and methanol, which are more expensive than the unit
price of biomass. In addition, to avoid the waste of CO gas in the WGS
unit, Cases 2-5 added a REH unit that consumes a lot of electricity to
generate green hydrogen, resulting in their utility costs being 3.40, 4.45,
2.94 and 3.61 times of Case 1. Because the flowsheet of Cases 2–5 is
simpler than that of Case 1, the other costs of Cases 2–5, including wages
Q. Yang et al. Journal of Cleaner Production 396 (2023) 136540

Fig. 16. Total capital investment (a) and its distributions of the conventional (b and c) the proposed (d and e) BtEG processes.

Table 3
Consumptions and costs of the raw materials and utilities of Cases 1-5.
Case 1 Case 2 Case 3 Case 4 Case 5

Item Unit price e Consumption Cost Consumption Cost Consumption Cost Consumption Cost Consumption Cost
Biomass a 115 $/t 841.92 100.19 417.36 49.67 405.76 48.29 380.64 45.30 409.84 48.77
Methanol a 461.5$/t 2.50 1.15 73.32 33.84 52.33 24.15 133.84 61.77 90.45 41.74
EO a 1384.6 $/t 0.00 0.00 49.91 69.11 35.62 49.32 91.11 126.14 61.57 85.25
Others 0.0031 0.0026 0.0027 0.0021
Total raw materials cost 101.35 152.61 121.76 233.21 175.77
Electricity b 0.1/0.062 $/kWh 311.60 31.16 1435.90 89.03 1918.17 118.93 1182.68 73.33 1500.31 93.02
Steam c 5.6 $/GJ 611.71 3.43 915.95 5.13 872.15 4.88 1389.09 7.78 1272.84 7.13
Water a 0.58 $/t 4950.49 2.87 2654.06 1.54 2674.68 1.55 2400.56 1.39 2624.36 1.52
Total utilities cost d 37.46 95.69 125.36 82.50 101.67

Note: a: the unit of consumption is 104 t/y; b: the unit of consumption is MWh/y; c: the unit of consumption is GJ/y; d: the unit of cost is M$/y, and e: the average price
in the recent three years.

and benefits, depreciation, and maintenance, are lower than those of
Case 1. Although the TPC of Cases 2–5 is increased, they can by-produce
more DMC and have higher income, which can improve the economic
benefit of Case 1, as discussed in the following section.
3.4.3. Comparison of NPV and IRR
The total income of Cases 1–5 is firstly calculated in terms of the
production and unit price of ethylene glycol and dimethyl carbonate as
shown in Table 4. The total income of Cases 2–5 is increased from 400 M
$/y to 550.86 M$/y, 507.67 M$/y, 675.39 M$/y, and 596.11 M$/y,
respectively. It is mainly because that Cases 2–5 can produce the same
amount of ethylene glycol product as Case 1, and produce lots of
dimethyl carbonate by-product simultaneously. The unit price of
dimethyl carbonate is higher than that of ethylene glycol, considering
the average market price in the recent three years. Therefore, the total
income of the proposed BtEG processes (Cases 2–5) are greatly increased
from 400 M$/y to 550.86 M$/y, 507.67 M$/y, 675.39 M$/y, and
586.11 M$/y, respectively. Case 4 has the highest net profit, 222.15 M
$/y, followed by Case 5, 184.16 M$/y, and Case 2, 181.44 M$/y.
Therefore, integrating renewable electricity for hydrogen production
and CO2 utilization technologies can significantly improve the economic
performance of the conventional BtEG process.
The NPV of Cases 1–5 is calculated by Eq. (25) since the total capital
investment, production cost, and income of the BtEG processes are
determined. Results indicate that the NPV of Case 4 is the highest,
1101.01 M$, which is 2.49, 1.43, 2.14, and 1.40 times higher than that
of Cases 1–3 and Case 5, respectively. Similar to the NPV’s results, the
IRR of Cases 1–5 presents the same sort. The IRR of Case 4 is the highest,
28.84%, followed by Case 5, 23.86% and Case 2, 23.63%. Case 1 is the
worst, with 17.56%. The main reasons are that Cases 2–5 can get the
same amount of ethylene glycol income as Case 1, but also a large
amount of DMC income from the CO2 reuse. In fact, the DMC income of
Cases 2–5 is about 1.38, 1.27, 1.69 and 1.47 times greater than the total
income of Case 1. Thereby, the total income and profit of Cases 2–5
processes are much higher than those of Case 1. Moreover, the total
capital investment of Cases 2–5 is greatly reduced compared with the
conventional BtEG process. Therefore, these results highlight that the
integration of renewable energy for hydrogen production and CO2

15
Q. Yang et al. Journal of Cleaner Production 396 (2023) 136540

are determined (shown in Table 5), their total GHG emissions are
calculated by Eq. (26). The detailed information on the GHG emissions
of raw material and utilities is indicated in Table S12 in Appendix B. The
negative value of the acquisition stage is because the amount of the
produced CO2 is less than that of the absorbed during the growth stage of
the biomass. In fact, the GHG emissions of the acquisition stage of Cases
1–5 is − 3.55 t/t, − 1.76 t/t, − 1.71 t/t, − 1.61 t/t, and − 1.73 t/t,
respectively. More CO2 absorbed in Case 1 is because that its input
biomass is much greater than Cases 2–5. Qiu et al. (2010) and Xu et al.
(2021) believed that the road transportation distance is 100 km when
carrying out a life cycle assessment on a biomass-based chemical pro­
cess. Therefore, the transportation method and distance of the BtEG
process are assumed as road and 100 km. Nevertheless, results indicate
the proportion of the GHG emissions caused by the transportation stage
of Cases 1–5 can be ignored, which is less than 0.04 t/t. As for the
production stage, due to the proposed Cases 2–5 integrated with the REH
and CDU unit can use renewable energy for hydrogen production and
reuse emitted CO2 for DMC and EG production, the GHG emissions of
this stage of Cases 2–5 are significantly decreased from 4.03 t/t to 0.15
Fig. 17. Distribution of total production cost of Cases 1–5. t/t, 0.18 t/t, 0.12 t/t, and 0.14 t/t, respectively. As a result, the total life
cycle GHG emissions of Cases 1–5 are 0.51 t/t, − 1.60 t/t, − 1.52 t/t,
− 1.47 t/t, and − 1.57 t/t, respectively. Therefore, from the perspective
Table 4 of the whole life cycle, the four proposed new processes can indeed
Total income, profit, and internal rate of return of Cases 1-5. achieve carbon reduction in comparison with the conventional process.
Case 1 Case 2 Case 3 Case 4 Case 5
4. Conclusions
EG production (t/ 4 × 105 4 × 105 4 × 105 4 × 105 4 × 105
y)
EG income (M$/y) 400.00 400.00 400.00 400.00 400.00 Four BtEG processes that integrate renewable energy for hydrogen
a
production and CO2 utilization are proposed to find the best strategy for
DMC production 0 1.03 × 0.74 × 1.88 × 1.27 × the carbon-neutral and cost-effective development of the ethylene glycol
(t/y) 105 105 105 105
DMC income (M 0 150.86 107.67 275.39 186.11
industry. The effect of different gasification agents on the performance
$/y) a of the BtEG processes is investigated and optimized with the aid of
Total income (M 400.00 550.86 507.67 675.39 586.11 whole-process modeling and simulation. The techno-economic-
$/y) environment performance of these proposed processes is evaluated
Total profit (M$/y) 205.95 241.92 198.20 296.20 245.55
and compared with the conventional process. The main conclusions
Net profit (M$/y) 154.46 181.44 148.65 222.15 184.16
Net present value 440.51 769.40 513.44 1101.01 787.94 obtained are as follows.
(M$)
Internal rate of 17.56% 23.63% 19.50% 28.84% 23.86% (a) The gasification agent has a great influence on the biomass
return (%) gasification process. O2 mixed with a certain amount of CO2 as a
a
The unit price of EG and DMC is 1000 $/t and 1461.54 $/t referring to their gasification agent is helpful to increase the production of CO in
average market price in the recent three years. the syngas, while mixing with steam is beneficial to increase the
production of H2 in the syngas. Therefore, the BtEG process with
utilization technologies is an economically favorable method to achieve O2 and CO2 gasification agents (Case 3) has the highest yield of
ethylene glycol carbon neutral production, especially in Case 4. CO, and the BtEG process with O2 and steam gasification agents
(Case 4) has the highest yield of hydrogen.
(b) The proposed BTEG processes integrated with the CO2 utilization
3.5. Environmental performance assessment
unit can significantly improve the element utilization efficiency
and exergy efficiency of the traditional process. For example, the
When the amounts of CO2, CH4, and N2O in each stage of Cases 1–5

Table 5
Life cycle GHG emissions of Cases 1-5.
Item Unit Acquisition Transportation Production Total GHG

Case 1 CO2 kg/t − 3.66E+03 3.10E+01 3.34E+03 − 2.95E+02 5.63 E+02

CH4 kg/t 3.30E+00 3.49E-02 2.96E+01 3.29E+01
N2O kg/t 1.06E-01 1.47E-04 9.02E-03 1.15E-01
Case 2 CO2 kg/t − 1.82E+03 1.54E+01 1.32E+02 − 1.67E+03 − 1.60E+03
CH4 kg/t 1.63E+00 1.73E-02 5.64E-01 2.22E+00
N2O kg/t 5.28E-02 7.29E-05 1.72E-04 5.30E-02
Case 3 CO2 kg/t − 1.77E+03 1.49E+01 1.69E+02 − 1.58E+03 − 1.52E+03
CH4 kg/t 1.59E+00 1.68E-02 5.47E-01 2.15E+00
N2O kg/t 4.89E-02 6.73E-05 1.67E-04 4.91E-02
Case 4 CO2 kg/t − 1.66E+03 1.40E+01 1.04E+02 − 1.54E+03 − 1.47E+03
CH4 kg/t 1.49E+00 1.58E-02 5.24E-01 2.03E+00
N2O kg/t 4.81E-02 6.65E-05 1.60E-04 4.84E-02
Case 5 CO2 kg/t − 1.78E+03 1.51E+01 1.31E+02 − 1.64E+03 − 1.57 E+03
CH4 kg/t 1.60E+00 1.70E-02 5.53E-01 2.17E+00
N2O kg/t 5.18E-02 7.16E-05 1.68E-04 5.20E-02

16
Q. Yang et al. Journal of Cleaner Production 396 (2023) 136540

carbon utilization efficiency of Cases 2–5 is increased from
39.30% to 78.26%, 80.36%, 82.50%, and 79.14%, respectively.
Moreover, their exergy efficiency is increased from 50.75% to
56.18%, 51.73%, 57.88%, and 54.20%, respectively.
(c) The proposed BTEG processes integrated with renewable elec­
tricity for hydrogen production can greatly reduce the total
capital investment. Integrating the CO2 utilization unit can by-
produce a large number of DMC products and greatly increase
the total income of the conventional process. As a result, the in­
ternal rate of return of Cases 2–5 is increased from 17.56% to
23.63%, 19.50%, 28.84%, and 23.86%, respectively. Thus, Case 4
has the best economic performance, followed by Case 5 and Case
2.
(d) Since the carbon emissions in the biomass acquisition stage are
negative and the CO2 in the production stage is reused by the CO2
utilization unit, the total life cycle GHG emissions of Cases 2–5
are reduced from 0.51 t/t to − 1.60 t/t, − 1.52 t/t, − 1.47 t/t, and
− 1.57 t/t, respectively. Therefore, from the perspective of the
whole life cycle, the four proposed new processes can indeed
achieve carbon reduction in comparison with the conventional
process.
In summary, the BtEG process with O2 and steam gasification agents
(Case 4) has the best comprehensive performance in the four proposed
and conventional processes. It provides a promising development di­
rection for the ethylene glycol industry to achieve the carbon neutrali­
zation target, and indicates the conventional chemical processes
integrated with renewable energy to hydrogen and CO2 to high-value-
added chemicals technologies have a promising application prospect.
However, for future industrial implementation, more Process System
Engineering methods should be employed to investigate and optimize
their global heat exchanger network and water network, analyze the
adaptability of raw biomass, investment risks and competitiveness with
the unpredictable market fluctuations.
CRediT authorship contribution statement
Qingchun Yang: Conceptualization, Funding acquisition, Writing –
review & editing. Yingjie Fan: Methodology, Investigation, Writing –
original draft. Jianlong Zhou: Software, Investigation, Resources,
Formal analysis. Lei Zhao: Methodology, Investigation, Data curation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
The authors are grateful for financial support from the National
Natural Science Foundation of China (No. 22108052), the Fundamental
Research Funds for the Central Universities (No. JZ2021HGTB0117),
and the open fund of Intelligent Interconnected Systems Laboratory of
Anhui Province (No. PA2021AKSK0110).

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://doi.org/10.1016/j.jclepro.2023.136540.

Nomenclature

a anode
αi activity of substance i
c cathode
CO2 ,m oxygen concentrations
CH2 ,m hydrogen concentrations
CD the depreciation cost
CM manufacturing cost
CGE general expense
COM other operating and maintenance cost
CR the cost of raw material
CU the cost of utilities
exch,o
i standard chemical exergy of ith species
Ex exergy
F mole flowrate
h molar enthalpy
Icell cell current
j current density
Keq reaction equilibrium constant
Q processing scale
r reaction rate
s molar entropy
V0 open circuit voltage at standard temperature and pressure
Vact activation overpotential
Vcell cell voltage
Vocv open circuit voltage
Vohm ohmic overpotential
Vpk,pyr pyrolysis product set

17
Q. Yang et al. Journal of Cleaner Production 396 (2023) 136540

x mole fraction of substance

Y yield
z the number of moles of electrons

Abbreviations
AGR acid gas removal
ASU air separation unit
AWE alkaline water electrolysis
BG biomass gasification
BtEG biomass to ethylene glycol
CDU carbon dioxide utilization
DMC diethyl carbonate
DMO diethyl oxalate
DMOS dimethyl oxalate synthesis
EG ethylene glycol
EGR ethylene glycol refining
EGS ethylene glycol synthesis
EI equipment investment
EO ethylene oxide
GHG greenhouse gas
HCS H2 and CO separation
IRR internal rate of return
MG methyl glycolate
MN methyl nitrite
NPV net present value
PEM proton exchange membrane electrolysis
REH renewable electricity for hydrogen production
RD reaction distillation
RF ratio factor
SOEC solid oxide electrolysis
TCI total capital investment
TPC total production cost
WGS water gas shift

Subscripts
ch physical
ph physical
tot total

Greek Letters
φ exergy efficiency
εC carbon utilization efficiency

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