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Energy 229 (2021) 120713

Contents lists available at ScienceDirect

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

Thermodynamic and techno-economic analyses of a novel integrated


process of coal gasification and methane tri-reforming to ethylene
glycol with low carbon emission and high efficiency
Qingchun Yang a, c, *, Simin Xu a, Jinliang Zhang a, Chenglin Liu a, Dawei Zhang a,
Huairong Zhou b, Shumei Mei c, Minglin Gao c, Hongyan Liu c
a
School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei, 230009, PR China
b
College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou, 730050, PR China
c
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

Article history: Coal to ethylene glycol technology has been fruitfully developed due to the abundant reserve of coal and
Received 14 January 2021 the low production cost. However, its sustainable development is plagued by the high CO2 emissions.
Received in revised form Hence, a novel coal to ethylene glycol process integrated with methane tri-reforming technology is
13 April 2021
proposed, simulated, and optimized for low carbon emission and high efficiency. The effects of the key
Accepted 16 April 2021
Available online 26 April 2021
operational parameters on the performance of the proposed process are analyzed and optimized along
with the established rigorous system modeling and simulation models. Results show the optimal ratio of
coke oven gas and coal of the proposed process is 95 kmol/t, the optimal ratio among CH4, CO2, H2O and
Keywords:
Coal to ethylene glycol
O2 of the tri-reforming unit is 1: 1.43: 2.15: 0.44, and its optimal temperature is 850  C. Compared with
Tri-reforming the conventional process, the carbon and exergy efficiencies of the proposed process are increased by
CO2 reduction 50.94% and 15.16%, the capital investment and production costs are saved by 16.1% and 14.3%, and the
Technoeconomic analysis direct CO2 emission is reduced by 98.06%. Therefore, it is a promising method for coal based chemical
Parametric optimization processes to integrate methane tri-reforming technology to save energy and reduce carbon emissions.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction glycol plant.


In view of the shortcomings of the oil-based and biomass-based
Ethylene glycol (EG) is considered as one of the most important routes, many countries endeavor to promote efficient exploration
platform chemicals. In particular, it is widely used for the manu- and exploitation of abundant coal resources for ethylene glycol
facture of polyesters, predominantly poly (ethylene terephthalate) production, especially China [7]. For example, there are more than
[1]. The annual production of EG is more than 25 million tons and 20 coal to ethylene glycol (CtEG) plants are successfully operated
the demand for EG is expected to grow at a rate of 5% per year [2]. and more than 30 new CtEG plants have been approved to build by
Currently, ethylene glycol is primarily produced from oil-based 2020 [4]. In addition, the total CtEG production capacity has
route; however, it suffers from high production cost, high energy exceeded 6 million tons per year. The most significantly advantages
consumption, and low efficiency because of the low yield of of the CtEG process are mature, low production cost, high yield of
ethylene oxide [3,4]. The use of biomass to ethylene glycol could target product, and simple flowsheet. Unfortunately, this process is
lead to lower CO2 emissions, however, there are additional prob- criticized by high CO2 emissions. As detailed discussed in our pre-
lems like biomass availability or the different H2/CO that it is vious works [8e10], the CO2 emission of a CtEG process built in
possible to obtain from biomass gasification [5,6]. As a result, there Inner Mongolia city is about 3.2 t/t-EG. The high CO2 emissions
is currently no large-scale industrialized biomass-to-ethylene leads to serious carbon resource loss and greatly weaken the eco-
nomic advantages if CO2 tax is considered. The main reason for the
high CO2 emissions of the conventional CtEG process is that coal is a
* Corresponding author. School of Chemistry and Chemical Engineering, Hefei
carbon-rich resource. As a result, the H2/CO ratio of syngas (0.5e1.0)
University of Technology, Hefei, 230009, PR China. is much less than that of the desired ratio for ethylene glycol
E-mail address: ceqcyang@hfut.edu.cn (Q. Yang).

https://doi.org/10.1016/j.energy.2021.120713
0360-5442/© 2021 Elsevier Ltd. All rights reserved.
Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

production (about 2.0) [11]. Thus, many precious CO gas is shifted to 2.1. The traditional CtEG process
be CO2 in the water gas shift (WGS) unit. Moreover, the WGS unit
consumes lots of fresh water, which also greatly increases the water The schematic diagram of the traditional CtEG process is present
consumption and indirect CO2 emissions of the CtEG process. in Fig. 1. Because the H2/CO ratio of the syngas from the coal gasi-
On the other hand, conversion and utilization of carbon dioxide fication (CG) unit is far less than the desired value, part of the
have gained significantly attention not only because CO2 has an syngas is sent to the water gas shift (WGS) unit to increase H2/CO
impact on global climate change, but also CO2 can be reused as an ratio. Then the acid gas removal (AGR) unit is used to remove the
important carbon resource for fuels and chemicals production CO2, sulfide, etc. The clean syngas from the AGR unit is fed into the
[12e14]. Tri-reforming technology, one of the most interesting hydrogen and carbon monoxide separation (HCS) unit, in which the
options, can use CO2 as a co-reactant to produce syngas and high-purity H2 and CO are obtained. The high-purity hydrogen is
chemicals. For example, Minutillo & Perna [15,16] proposed a novel used to the hydrogenation of dimethyl oxalate (DMO) in the
integrated co-generation of power and syngas system for treatment ethylene glycol synthesis (EGS) unit for the ethylene glycol pro-
of CO2 from fossil fired power plants. They found that the novel duction; while the high-purity CO is used to synthesize DMO in the
process can reduce CO2 emission by 84%. Zhang et al. [12] studied a dimethyl oxalate synthesis (DMOS) unit [9]. The high-purity EG
methanol synthesis process via tri-reforming to treatment of CO2 in product is finally obtained after the ethylene glycol refining (EGR)
flue gases, and this process is further improved and optimized by unit. More detailed description of the traditional CtEG process can
Dwivedi et al. [17]. Zhang et al. [18] also developed an integrated be found in our previous work [9].
process of dimethyl ether production with tri-reforming. Results
show that tri-reforming coupled to dimethyl ether synthesis is an 2.2. The feature of the novel Tri-CtEG process
economically feasible approach for the treatment and utilization of
CO2 in flue stack gases [18]. Qian et al. [19] integrated coke oven gas To simultaneously reduce and utilize the CO2 of the traditional
tri-reforming and coal gasification for methanol production. The CtEG process, the Tri-CtEG process is integrated with a new tri-
results show that the CO2 emission of the new process is reduced by reforming of methane (TRM) unit and reduced a water gas shift
44%, the carbon utilization and energy efficiencies are increased by (WGS) unit as shown in Fig. 2. The input CH4 of the TRM unit is
25% and 10% in comparison with a conventional coal to methanol supplied by low-price coke oven gas (COG). It is mainly because
process. Damanabi [20] improved a gas-to liquid process by CO2 that: (1) COG is a hydrogen-rich gas that mainly consists of H2
utilization in tri-reforming reactor. Sadeghi et al. [21] conducted (58e60%) and CH4 (23e27%) [25], thus it can simultaneously pro-
detailed exergoeconomic assessment and optimization of a syngas vide CH4 and additional H2 to adjust H2/CO ratio; (2) it is greatly
production system with a desired H2/CO ratio based on methane cheaper and more helpful to decrease the production cost in
tri-reforming process. comparison to natural gas because it is regarded as the exhaust gas
Different from other reforming technologies, the tri-reforming of the coking industry; (3) it is available and stable source since
has many advantages [12,22,23]: (1) it integrates CO2 reforming, China’s annual COG production is more than 7  1010 m3, which is
steam reforming and partial oxidation of methane into one reactor; only used as a waste; and (4) it is a win-win result of the CtEG and
(2) it does not need to purify the feedstock which can greatly coking industries because most of the COG is directly combusted or
reduce energy consumption and production cost; (3) the additions discharged, resulting in economic lost and environmental
of O2 and steam are helpful to reduce carbon deposition onto pollution.
catalyst; and (4) the H2/CO ratio of syngas is easily controlled to the In comparison with the CtEG process, the most significant fea-
desired ratio for chemicals production [24]. Therefore, the tri- tures of the Tri-CtEG process are as follows: (1) the Tri-CtEG process
reforming technology is regarded as an effective and energy- adds two new units, the TRM and COG separation (COGS) units, and
efficient way to alleviate and utilize CO2 emission. To data, how- reduces a WGS unit; (2) the H2/CO ratio of the syngas is adjusted by
ever, there is no reported work has been conducted to analyze the the TRM unit and the flowrate of COG rather than by a WGS unit; (3)
feasibility of integration the tri-reforming technology into the the CO2 emission of the CtEG process is reused to produce syngas
conventional CtEG process for simultaneous reduction and utili- rather than discharged as a pollutant; and (4) because the CO of the
zation of CO2 emission. syngas is not converted to CO2 and the produced CO2 is reused in
Since CtEG process discharges lots of CO2, the tri-reforming the Tri-CtEG process, the novel process has a great potentials for
technology can be integrated to use CO2 for syngas production. improving the carbon and energy efficiencies, economic perfor-
Thus, in this study, an integrated coal to ethylene glycol process mance as well as for reducing CO2 emission.
with methane tri-reforming technology (Tri-CtEG) is developed
and simulated via Aspen Plus software. The effects of the key 2.3. Modeling and simulation of the whole Tri-CtEG process
operational parameters on the performance of the proposed pro-
cess are investigated and optimized. A detailed technical and eco- The whole flowsheet of the Tri-CtEG process is designed and
nomic analysis is performed to show the promising advantages of modeled by the Aspen Plus due to it is one of the most common
the Tri-CtEG process in comparison with the conventional CtEG tools for steady-state modeling and simulation of chemical and
process. energy systems [26]. Besides, the kinetic model of chemical reac-
tion is simulated by embedded FORTRAN subprogram to improve
reliability. The key parameters for the modeling and simulation of
the Tri-CtEG process are list in Table 1. The basic property param-
eters of the input coal and COG are shown in Tables 2 and 3. The
2. Process description and modeling of the Tri-CtEG process simplified simulation flowsheet of the Tri-CtEG process is shown in
Fig. 3. It is mainly included nine units: the ASU, CG, AGR, COGS,
To identify the difference between the CtEG and the Tri-CtEG TRM, HCS, DMOS, EGS and EGR units. Due to the coal gasification
processes, a brief description of the conventional CtEG process is unit is a complicated and important unit, a detailed modeling and
indicated prior to the Tri-CtEG process. Then, the whole flowsheet simulation diagram of this unit is indicated in Fig. S1. The modeling
of the Tri-CtEG process is modeled and simulated in the aid of and simulation of the ASU, AGR, and HCS units is relatively simple,
simulator, Aspen Plus. which can refer to the references [11,27e30] and Fig. 3. Therefore,
2
Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

Fig. 1. Schematic diagram of the traditional CtEG process.

Fig. 2. Schematic diagram of the novel Tri-CtEG process.

Table 1
Main simulation parameters and assumptions [9,31e33].

Unit Parameter Value* Parameter Value*

ASU unit O2 supplied mole purity 99.8% N2 supplied mole purity 99.9%
CG unit Gasification pressure 4.0 MPa Gasification temperature 1500  C
Oxygen to coal 0.42 Steam to coal 0.25
AGR unit Pressure 3.3 MPa Temperature 40  C
Methanol (make up) 0.04 t/h N2 (Purge gas) 12.50 t/h
HCS unit H2 recovery ratio 95.17% CO recovery ratio 91.75%
DMOS unit Reaction temperature 130  C Pressure 0.5 MPa
Regeneration temperature 40  C Theoretical plates 23
EGS unit Reaction temperature 235  C Pressure 3.0 MPa
Reaction temperature 40  C H2/DMO (mole ratio) 42
EGR unit Recovery column temperature 90  C Pressure 0.1 MPa
Methanol recovery ratio 99.5% DMC removal ratio 95.2%
COGS unit Desulfurization reactors 350  C Desulfurization reactors 2.5 MPa
Fe2O3/ZnO bed temperature 300  C Fe2O3/ZnO bed pressure 2.0 MPa
TRM unit Reaction temperature 850  C Pressure 0.1 MPa

this study is focused on the description of the modeling and fine desulfurization [26]. With the development of the AG2S
simulation of the COGS, TRM, EGS and EGR units. technology, which allows to convert H2S and CO2 into syngas
[34,35], it could be more suitable integrated to this process. Under
the high temperature condition, the sulfides are firstly reacted with
2.3.1. COGS unit
the catalyst and converted to H2S, and then a desulfurizer are used
Because the sulfides contained in the input COG are the poisons
to remove H2S [36]. The purified COG is fed to the TRM unit to
of the catalysts of methane reforming and EGS synthesis reactions
produce syngas and hydrogen.
[25], this study introduces the two-stage iron-molybdenum
hydrodesulphurization technology to remove the impurities of the
COG, which is modeled by a RStoic model. The most important 2.3.2. TRM unit
advantages of this technology are maturity and widely used to COG The clean COG feedstock enters the PSA separator to separate
3
Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

Table 2 minimization of Gibbs free energy (RGibbs) model is used to model


Proximate and elementary analysis results of the input coal. and simulate this reactor.
Properties Item value The standard molar enthalpy of reaction at any temperature can
Proximate analysis (wt. %) Ash 21.97
be formulated as follows:
Fixed carbon 57.86
Moisture 28.4 ð
Volatile matter 35.14 q ðTÞ ¼ DH þ D C q dT
Dr Hm (1)
0 r p
Elementary analysis (wt. %, dry-basis) Carbon 75.82
Oxygen 13.36
Hydrogen 5.54
Nitrogen 1.17 q ¼ Da þ DbT þ DcT 2
DCp;m (2)
Sulfur 0.60

where Dr Hmq ðTÞ and C q are the standard molar enthalpy of reac-
p;m
tion and constant pressure specific heat capacity.
Table 3
Basic parameters of the input COG.
After integration of Eq. (1), it is changed to be Eq. (3).

Component H2 CH4 CO CO2 N2 Others . .


q ðTÞ ¼ DH þ DaT þ DbT 2 2 þ DcT 3 3
Dr Hm (3)
Reference range [26] 55e60% 23e27% 5e8% 2e5% 3e5% <3% 0
This study 59% 26% 6% 3% 4.7% 1.3%
If substituting Eq. (3) into the differential of the Gibbs-
Helmholtz formula, the differential and integral equations are ob-
hydrogen and methane. The obtained CH4 is mixed with steam, tained as shown in Eqs. (4) and (5).
oxygen, and CO2 (recycled from the AGR unit) and fed into the TRM
ð   ð  q
reactor where is a synergetic combination of steam reforming of Dr Gqm Dr Hm
methane, dry reforming of methane, and partial oxidization of d ¼  d (4)
T T
methane. The main reactions occurred in the TRM reactor are
shown in Table 4. The TRM reaction involves a large number of
. .
input component variables, which greatly affects the yield of Dr Gqm ¼ DH0  DaT ln T  DbT 2 2  DcT 3 6 þ IT (5)
products and the heat balance. Therefore, in this paper, the ther-
modynamic equilibrium method is used to analyze the thermo-
dynamic conversion behavior of the TRM reactor. The Pen-Rob where Dr Gqm is the standard molar Gibbs energy of reaction; and I is
equation method is selected as the physical property method. A the integral constant. Due to Dr Gqm ¼ RT ln K q , the reaction
equilibrium constant (Kq) can be expressed as follows:

Fig. 3. Simulation flowsheet of the novel Tri-CtEG process.

4
Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

Table 4
Main reaction occurred in the TRM reactor.

No. Reaction △H298 (kJ/mol) No. Reaction △H298 (kJ/mol)

R1 CH4 þ CO2 ¼ 2H2þ2 CO 246.97 R8 COþ3H2 ¼CH4þH2O 205.80


R2 CH4 þ H2O ¼ COþ3H2 205.80 R9 C þ H2O ¼ CO þ H2 131.28
R3 CH4 þ 0.5 O2 ¼ CO þ 2H2 36.01 R10 C þ CO2 ¼ 2 CO 172.45
R4 CH4 þ 2 O2 ¼ CO2 þ 2H2O 802.62 R11 C þ O2 ¼ CO2 393.51
R5 CO þ 0.5 O2 ¼ CO2 282.98 R12 CH4 ¼ C þ 2H2 74.52
R6 H2 þ 0.5 O2 ¼ H2O 241.81 R13 2 CO ¼ C þ CO2 172.45
R7 CO þ H2O ¼ CO2 þ H2 41.17

DH0 Da ln T DbT DcT 2 I 2CH3 ONO ðMNÞ þ CO/DMC þ 2 NO (10)


ln K q ¼  þ þ þ  (6)
RT R 2R 6R R  
According to the thermodynamic property of materials (shown 43505 1 0:1
r ¼ 0:03815 exp  PNO PO2 (11)
in Table 5), the equilibrium constant of the R1-R13 occurred in the RT
TRM reactor can be calculated and modeled. The output of the TRM
reactor is exchanged heat with feed gas and steam to recover waste
heat by using the HEATX models. The syngas produced from this 2.3.4. EGS unit
unit is firstly mixed with the syngas produced from the coal gasi- The DMO from the DMOS unit enters the EGS reactor after
fication unit, and then is fed to the AGR unit to remove acid gas. mixed with hydrogen and preheated. The DMO hydrogenation re-
action is a consecutive reaction to synthesize ethylene glycol: DMO
2.3.3. DMOS unit is firstly reacts with hydrogen to produce methyl glycolate (MG),
The process of dimethyl oxalate synthesis via CO gaseous phase and MG then continues to hydrogenate to produce EG as shown in
coupling reaction involves two reactions: CO coupling reaction to Eqs. (12) and (13). However, EG will be excessively hydrogenated to
produce DMO and methyl nitrite (MN) regeneration reaction [37]. produce a small number of impurities (such as ethanol, water and
After compressed and preheated, the high-purity CO stream from 1,2-propanediol) during practical operation.
the HCS unit mixed with the recycle gas from the reactive distil-
lation column is sent to the DMOS reactor. Under the conditions of DMO þ 2H2 /2MG þ CH3 OH (12)
120  C and 0.5 MPa, CO is reacted with the methyl nitrite to produce
DMO in this reactor. The main reactions are shown in Eqs. (7) and MG þ 2H2 /2EG þ CH3 OH (13)
(8). A kinetic-based reactor model, RCSTR model, is applied for
modeling the DMOS reactor. The selected kinetic equation is based Because the EG synthesis reaction belongs to the kinetic control
on Pd/Al2O3 catalyst as reported on the works of Liu et al. [38] and Li reaction, so a kinetic-based reactor model, RPLUG model, is used to
et al. [37] as shown in Eq. (9). The output stream of the DMOS unit model the hydrogenation of DMO [32]. The related kinetic equa-
gets into the methanol packing absorption tower for separation. tions are shown in Eqs. (14) and (15). The detailed kinetic param-
The non-condensable gas containing NO at the top of the column is eters are list in Table S1 in the Supplementary material.
sent to the reactive distillation column for reusing. The bottom  
stream is fed to the atmospheric and pressurized columns to obtain k1 KDMO PDMO PH  PMG PMeOH
K p PH 1
high-purity DMO. rMG ¼
ð1þKDMO PDMO þKMeOH PMeOH þKMG PMG þKEG PEG þKET PET Þ
2CH3 ONO ðMNÞ þ 2 CO/DMO þ 2 NO (7) (14)
 
2CH3 ONO ðMNÞ þ CO/DMC þ 2 NO (8)
k2 KMG PMG PH  PEG PMeOH
Kp PH
2
rEG ¼
Ka Kb p2CO p2pMN ð1þKDMO PDMO þKMeOH PMeOH þKMG PMG þKEG PEG þKET PET Þ
rDMO ¼ . (9)
Ka p2pMN þ Ka Kb p2pCO p2pMN Kc þ Kb p2pCO (15)
The mixture out from the EGS reactor goes to the separator
The recovered methanol is reused to produce methyl nitrite in (FLASH model) to separate unreacted hydrogen and crude EG at the
the regeneration tower as shown in Eq. (10). This process is conditions of 40  C and 0.5 MPa. The obtained hydrogen is recycled
modeled by a REAC-DIST model and its kinetic can be written as Eq. to the EGS reactor, and the crude EG is further separated to obtain
(11) [37]. satisfactory EG products in the EGR unit.

Table 5 2.3.5. EGR unit


Thermodynamic property of the materials. As mentioned above, the crude ethylene glycol from the EGS
unit contains a small number of impurities. Thus, it needs to be
Component Hm, 298 Gm,298 a b c
upgraded and refined to meet the quality requirements of down-
CH4 74.52 50.49 14.15 75.496 17.99
stream products. In the EGR unit, the crude ethylene glycol is sent
CO2 393.51 394.37 26.75 42.258 14.25
H2O 241.814 228.59 29.16 14.49 2.022 to the methanol recovery column to recover methanol, which is
O2 0 0 28.17 6.297 0.7494 modeled by a RADFRAC model because it can perform rigorous
H2 0 0 26.88 4.347 0.3265 calculations on column [32]. The bottom of this column is then fed
CO 110.53 137.15 26.537 7.6831 1.172 to the dehydration and dealcoholized columns to remove water and
C 0 0 17.7 3.685 11.68
alcohols. The EG-rich stream finally enters the EG product column
5
Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

to obtain high-purity EG with 99.8 wt% by a design specification [8]. (APEA) software. It is a software linked to Aspen Plus to estimate
costs on the basis of the simulation results. Considering the costs
3. Methodology are related to the local situation, thus the China is set as the default
country, which means that several assumptions (such as salary
To demonstrate the promising advantages of the Tri-CtEG pro- rates, price of raw material and product, and currency) of economic
cess, the technical, economic and environmental analysis is costs are made in APEA software [42]. The main assumptions for
conduct in this study. calculation of total capital investment (TCI) and total production
coat (TPC) are shown in Table 6.
The TCI is comprised of the fixed and working capital in-
3.1. Technical analysis method
vestments. The working capital investment is set to be 15% of TCI
[7]. The required capital investment required to build the plant is
3.1.1. Carbon utilization efficiency
assumed to be borrowed and repaid over the plant lifetime (20
The carbon efficiency (CE) is the ratio of output and input
years) at a loan interest rate of 10% per annum [42].
effective carbon components of a process [19]:

2F out 3.2.2. Total production cost


CE ¼ . EG  100% (16) The total production cost (TPC) of the CtEG and Tri-CtEG pro-
uC min
coal
12 þ yC FCOG
in
cesses consists of capital annuities and operational costs as shown
in Eqs. (21) and (22) [10].
where min
coal
and uC mean the mass flowrate and fraction of carbon
in ACI þ CO&M þ Cfuel þ Cpower þ Clabor
element of input coal; FCOG and yC are the mole flowrate and TPCEG ¼ (21)
EG production
fraction of input COG.

3.1.2. Exergy efficiency ið1 þ iÞN


ACI ¼ TCI  CRF ¼ TCI  (22)
Exergy analysis, a powerful tool for determining the magnitude, ð1 þ iÞN  1
location, source and type of inefficiencies of a process, is used to
analyze the thermodynamic performance of the Tri-CtEG process where TPCEG is the production cost of ethylene glycol; CO&M , Cfuel ,
[39]. In this method, both the quality and quantity of energy are Cpower , and Clabor indicate the cost of fixed operation and mainte-
considered, which help to get more accurate and reliable results nance, fuel, power, and labor; ACI means the annuity of the capital
than energy analysis. The concept of exergy is based on the Second investment; i and N are the interest rate and the lifetime of the
Law of Thermodynamics and defined as the maximum available project.
work during a process that brings the system into equilibrium with
its environment [39]. As to a steady-state system, the exergy of a 3.2.3. Return on investment
stream (Ex) mainly consists of physical (Exph) and chemical exergy A sensitivity analysis was performed to evaluate the ability of
(Exch) as shown in Eq. (17) [40]: the process to withstand changes in feedstock and product values.
The return on investment (ROI) is used to evaluate the potential
Ex ¼ Exph þ Exch (17) profitability of the process and calculated as follows [44]:

where Exph and Exch are the physical and chemical exergy. annual after  tax profit
ROI ¼  100% (23)
After calculating the exergy of each stream, the exergy balance total captial investment
of the system can be established as shown in Eq. (18) [40]. Ac-
cording to the exergy balance, exergy efficiency (f), one of the most
important indicators used to assess the thermodynamic perfor-
3.3. Environmental analysis method
mance of a system, is defined as the ratio of the total exergy of the
target product and input [41] as shown in Eq. (19).
CO2 emission reduction and reuse are two of the main objectives
of this study. Therefore, the CO2 emission for EG production (mCO2)
Exergy balance of whole process Extot
in ¼ Extot
prd þ Extot
des þ Extot
others
of the CtEG and Tri-CtEG processes is conducted to identify the
(19)

Table 6
Extot
prd Economic assumptions in Aspen Process Economic Analyzer [43].
Exergy efficiency f ¼  100%
Extot
in Item Economic parameter Assumption
ExEG
¼  100% (20) General parameters Plant life 20 years
Excoal þ ExCOG þ Exutilities Base year 2017
Annual operating hours 8000 h
where subscript in, prd, des and others are the exergy of input, Loan interest rate 10%
Contingency 5%
product, destruction and others, respectively; ExEG is the output
Tax 25%
exergy of ethylene glycol; and Excoal , ExCOG , and Exutilities mean that Working capital 15% of TCI
the input exergy of coal, COG, and utilities. Raw material prices Coal 70.07 $/t
COG 0.07 $/m3
DMOS catalyst 26.28 $/kg
3.2. Economic analysis method EGS catalyst 36.50 $/kg
TR catalyst 28.47 $/kg
3.2.1. Total capital investment PSA packing 0.99 $/kg
The capital and operating costs of the CtEG and Tri-CtEG pro- Utilities prices Electricity 0.10 $/kWh
Cooling water 0.45 $/m3
cesses are estimated via the Aspen Process Economic Analyzer
6
Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

efficiency of CO2 reduction of the Tri-CtEG process. The CO2 emis- in Fig. 4 (a)e(c).
sion for EG production (mCO2) can be defined as the ratio of the total As Fig. 4(a) and (b) shown, increasing the CH4/CO2 ratio is
CO2 emission and the EG production (mEG) of a process [25]: obviously helpful for increasing the mole flowrate of H2 and CO
products; while increasing the H2O/CO2 ratio is helpful to increase
P
9
the mole flowrate of H2 but decrease that of CO products. The main
mCO2; i
total CO2 emission i¼1 reasons are that when the CH4/CO2 ratio is increased, more and
mCO2 ¼ ¼ (24) more CO2 are reacted with CH4 to produce CO and H2 (CO2 þ CH4 ¼
EG production mEG
CO þ H2). Furthermore, increasing the input steam helps to react
where mCO2; i is the mass flowrate of CO2 emission of ith unit. with CH4 to produce H2 and CO (H2O þ CH4 ¼ CO þ 3H2). Due to the
water gas shift reaction (CO þ H2O ¼ CO2 þ H2), increasing the H2O/
4. Results and discussion CO2 ratio is more helpful to produce H2 and consume CO. However,
the mole flowrate of H2 and CO is increased slightly when the CH4/
4.1. Optimization of key operational parameters CO2 ratio is higher than 0.7 because CO2 is completely reacted with
CH4. As Fig. 4 (c) shown, there is almost no CH4 in the output of the
To ensure that the novel Tri-CtEG process operates under the TRM reactor when the CH4/CO2 ratio is less than 0.7. It is mainly
best conditions, the key parameters are investigated and optimized because that input CH4 is completely converted to produce syngas.
in this study. However, when continuing to increase the CH4/CO2 ratio, more and
more CH4 cannot be converted effectively, resulting in a waste of
resources. Therefore, the optimal CH4/CO2 ratio is suggested to be
4.1.1. Interaction effect of CH4/CO2 and H2O/CO2 ratios
0.7.
The composition of the feedstock to the TRM reactor greatly
affects the conversion of raw materials and product distribution.
Thus, the interaction effect of the CH4/CO2 and H2O/CO2 ratios on 4.1.2. Interaction effect of COG/coal and H2O/CO2 ratios
the performance of the TRM reactor are investigated and indicated The H2/CO ratio is one of the most important parameters for

Fig. 4. Interaction effect of CH4/CO2 and H2O/CO2 ratios on the performance of the TRM reactor.

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Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

ethylene glycol production. It significantly depends on the input Therefore, the effect of temperature on the ln Ki of reactions R1-R13
ratio of the COG, coal, and steam. Therefore, the effect of the COG/ and the reaction performance of the TRM unit as shown in Fig. 6(a)
coal and H2O/CO2 ratios on the H2/CO ratio of syngas produced from and (b).
the TRM unit and the Tri-CtEG process are investigated and opti- As Fig. 6(a) shown, when the temperature is increased, the ln Ki
mized as shown in Fig. 5 (a) and (b). It should be noted that the of the endothermic reactions, R1, R2, R9, R10, and R12, is gradually
syngas produced from the Tri-CtEG process includes three parts: (i) increased, while the ln Ki of the exothermic reactions, R3-R8, R11,
the syngas produced from the TRM unit; (ii) the syngas from the CG and R13, is gradually decreased. It is mainly because that increasing
unit; and (iii) the high-purity H2 from the COGS unit. the temperature has a positive effect on the endothermic reaction
It can be seen that the H2/CO ratio of both the output gas of the according to the Le Chatelier’s Principle. The greater the equilib-
TRM unit and the Tri-CtEG process is gradually increased when the rium constant of chemical reaction, the greater the thermodynamic
COG/coal and H2O/CO2 ratios are increased as shown in Fig. 5 (a) competitiveness of chemical reaction. Thus, the equilibrium con-
and (b). It is mainly because that increasing the COG/coal ratio stant of each combustion reaction is large, because combustion
means the mole flowrate of COG is increased, which helps to take reactions are the fastest reactions in the TRM reactor as shown in
place of reactions R1-R3. Thus, the H2/CO ratio of the TRM unit is Fig. 6(a). Furthermore, the reforming temperature has a direct ef-
gradually increased along with the increase of COG/coal ratio. fect on thermodynamic competitiveness of reactions R1-R13. As a
However, it is not obviously changed when the COG/coal ratio is result, the thermodynamic competitiveness of each reaction pre-
higher than 100 kmol/t as shown in Fig. 5(a). sents different results in different temperature ranges, and the
When COG/coal and H2O/CO2 ratios are increased, the H2/CO sequence of competitiveness of the above reactions is: at low
ratio of the Tri-CtEG process is increased from 0.64 to higher than temperatures, R4> R11 > R5 > R6 > R3 > R8 > R13 > R7
2.0 as shown in Fig. 5(b). Furthermore, COG/coal ratio has a greater > R12 > R9 > R10 > R2 > R1; and at high temperatures, R4 > R11 >
effect on the H2/CO ratio of the Tri-CtEG process than H2O/CO2 R3 > R6 > R5 > R1 > R2 > R10 > R12 > R9 > R7 > R13 > R8.
ratio. It is mainly because that COG is a hydrogen-rich gas. The effect of the temperature on the mole flowrate of products
Increasing the COG/coal ratio will greatly increase the production of and the H2/CO ratio of the TRM unit is shown in Fig. 6(b). The mole
the high-purity H2 from the COGS unit. As a result, it could greatly flowrate of CH4 is greatly decreased along the increase of temper-
increase the H2/CO ratio of the Tri-CtEG process. Compared with ature. It is mainly because that more and more CH4 are converted
the results of H2O/CO2 ratio increases from 1.0 to 1.5 and 1.5 to 2.0, into syngas by reactions R1 and R2. Moreover, CH4 is completed
it has a less impacts on increasing the H2/CO ratio of the TRM unit reacted to produce syngas when the temperature is higher than
and the CtEG process. Thus, the H2O/CO2 of the TRM is suggested to 850  C. Because the reaction R13 is easy to happen at low tem-
be 1.5 in this study. perature, so the mole flowrate of CO2 is slightly increased when the
To fully utilize input CO2 and CH4 as well as increase the pro- temperature increases from 400  C to 500  C. However, when the
duction of H2 and CO products, the optimal COG/coal ratio of the temperature is higher than 500  C, more and more CO2 are reacted
Tri-CtEG process is set to be about 95 kmol/t since the CH4/CO2 and with CH4 and C to produce syngas. As a result, the mole flowrate of
H2O/CO2 ratios are determined to be 0.7 and 1.5. According to the CO2 is obviously decreased as the temperature increased. It can be
previous works [11,20], the optimal O2/CO2 ratio is 0.31. Thus, a seen that the mole flowrate of H2 and CO is greatly increased when
reasonable CH4: H2O: CO2: O2 of the Tri-CtEG is suggest to the temperature is lower than 850  C. But it is almost no change
1:1.43:2.15:0.44. when the temperature is higher than 850  C. The H2/CO ratio of the
syngas produced by the TRM unit is gradually decreased with the
increase of temperature. When the temperature is higher than
4.1.3. Effect of reforming temperature
850  C, the mole flowrate of products and the conversion of raw
The reforming temperature of the TRM reactor significantly af-
materials are almost no change. Therefore, the optimal temperature
fects the reaction rate and extent of R1-R13 (shown in Table 4).

Fig. 5. Interaction effect of COG/coal and H2O/CO2 ratios on the H2/CO ratio of (a) the TRM unit and (b) the Tri-CtEG process.

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Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

4.3. Technical performance

The carbon efficiency and exergy efficiency are conducted to


analyze the technical performance of the Tri-CtEG process.

4.3.1. Carbon efficiency


The carbon efficiency of the CtEG and Tri-CtEG processes are
calculated in terms of their carbon balances. Compared with the
conventional CtEG process, the carbon efficiency of the Tri-CtEG
process is significantly increased from 21.23% to 72.17%. It is
mainly because that: (1) the proposed Tri-CtEG process does not
need water gas shift unit, thus 49.05% of the syngas produced from
the coal gasification unit does not convert into CO2, in fact, it is used
to synthesis ethylene glycol product in the Tri-CtEG process; (2) to
produce the same amount of syngas, the carbon efficiency of the
TRM unit is much higher than that of the CG unit; and (3) the CO2
emissions of the CtEG process are completely reused in the Tri-CtEG
process since the related parameters are optimized in this study.

4.3.2. Exergy efficiency


The thermodynamic performance of the CtEG and Tri-CtEG
processes is performed according to the Eq. (20) as shown in
Fig. 7(a)e(c). The exergy of the target product of the CtEG and Tri-
CtEG processes is same and equals to 397.8 MW; however, their
total input exergy is quite different, 1296.8 MW and 855.5 MW, as
show in Fig. 7(a) and (b). As a result, the exergy efficiency of the
CtEG and Tri-CtEG processes is 30.68% and 45.84%. The ratio of
exergy destruction of the Tri-CtEG process is decreased from
54.66% to 42.67% in comparison of that of the CtEG process. It is
mainly because the TRM unit is a more efficiency method to pro-
duce syngas than the coal gasification technology. Moreover, the
Tri-CtEG process has better resource utilization efficiency as well as
less emissions than those of the CtEG process. As a result, the
technical performance of the Tri-CtEG process is much better than
that of the conventional CtEG process.

4.4. Economic performance


Fig. 6. Interaction effect of reforming temperature on the (a) the ln Ki of reactions and
(b) the TRM unit. In this paper, the total capital investment (TCI), total production
cost (TPC), and return on investment (ROI) are conducted to show
the economic performance of the CtEG and Tri-CtEG processes.
of the TRM unit is to 850  C.
4.4.1. Total capital investment
The total capital investment of the CtEG and Tri-CtEG processes
4.2. Simulation results and validation is estimated according to the established models in the Section 3.3.
They are 2552 and 2141 $/t-EG. The TCI of the Tri-CtEG process is
Referring to the above built models and the main operational saved by 16.11% compared with the CtEG process. The proportion of
parameters indicated in Table 1, the whole flowsheet of the Tri- investment cost of each unit to the TCI is shown in Fig. 8. As to the
CtEG process is simulated. The key parameters of the main CtEG process, the ratio of the capital costs of the coal gasification
streams are obtained and shown in Table 7. The Tri-CtEG process section, which involves the CG, WGS and ASU units, is about 26% of
consumes 42.31 t/h coal and 4019.86 kmol/h COG to produce the TCI. The ratio of the syngas separation and purification section,
75.02 t/h EG products. The total input syngas of Tri-CtEG process is which consists of the AGR and HCS, is about 23% of the TCI. The ratio
about 7269.23 kmol/h, of which 68.10% is produced from the TRM of the EG production section, which involves DMOS, EGS and EGR
unit. The CO2 capture ratio of the AGR unit is about 90.34%. units, is about 51% of the TCI. Therefore, the established economic
Moreover, in order to ensure the reliability of the established models are reasonable since those ratios of an operating CtEG plant
models and the simulation results, the key parameters of the Tri- designed by China Wuhuan Engineering Co., Ltd. are about 21%, 21%
CtEG process are analyzed and compared with the actual indus- and 58% of the TCI, respectively [4]. Compared with the CtEG pro-
trial data as shown in Figs. S2 and S3 in the Supplementary Mate- cess, the ratio of the capital costs of the coal gasification section and
rial. The results show that the simulation of the mole fractions of the syngas separation and purification section are decreased by 14%
the components in the key streams, intermediate and target and 7%; while that of the EG production and the TR section is
products are in good agreement with the industrial data. Thus, the increased by 8% and 13%. It is mainly because that the proposed Tri-
established models and the simulation results can be used to CtEG process does not need a WGS unit and the input CO2 of the
analyze the technical and economic performance of the Tri-CtEG AGR unit is greatly decreased. But there is an additional TRM unit in
process. the Tri-CtEG process.
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Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

Table 7
Main simulation results of the key stream of the Tri-CtEG process.

No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14

T ( C) 25 25 350 120 350 35 110 850 35 206 35 40 40 25


P (MPa) 0.1 0.1 1 2 1 0.1 0.1 0.1 0.6 3.85 0.1 0.8 2.6 0.1
M (t/h) 42.31 40.59 38.38 4.70 33.69 60.54 148.73 98.73 52.43 52.76 151.49 71.29 10.23 75.02
F (kmol/h) 4019.86 3939.26 2348.06 1591.2 1380.93 5651.77 4950.45 1638.9 2318.78 7269.23 2546.31 5056.86 1211.25
Mole fraction (%)
H2 0.00 59.00 59.91 100.00 0.74 0.00 0.21 46.01 0.00 27.37 40.06 0.01 99.91 0.00
H2O 0.00 0.00 0.00 0.00 0.00 0.00 39.56 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CO 0.00 6.00 6.09 0.00 15.08 0.00 4.25 24.95 0.00 59.58 36.00 99.06 0.05 0.00
CO2 0.00 3.00 3.05 0.00 7.54 99.00 26.31 24.91 0.00 12.09 20.82 0.00 0.00 0.00
CH4 0.00 26.00 26.40 0.00 65.36 0.00 18.40 0.65 0.00 0.68 0.66 0.00 0.00 0.00
O2 0.00 0.00 0.00 0.00 0.00 0.00 8.10 0.00 99.85 0.00 0.00 0.00 0.00 0.00
N2þAr 0.00 4.70 4.56 0.00 11.28 0.70 3.18 3.48 0.15 0.00 2.37 0.93 0.04 0.00
Others 0.00 1.30 0.00 0.00 0.00 0.30 0.00 0.00 0.00 0.28 0.09 0.00 0.00 0.13
EG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 99.87
Coal 100.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ex 183.80 461.87 459.40 155.67 263.46 7.75 277.13 261.45 1.85 154.61 416.07 195.82 335.16 397.80

*: The number of the key stream is marked in Fig. 3.

Fig. 7. Thermodynamic performance of the CtEG and Tri-CtEG processes.

Fig. 8. Distribution of the TCI of the CtEG and Tri-CtEG processes.

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Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

4.4.2. Total production cost


According to the Eqs. (21) and (22), the total production cost of
the CtEG and Tri-CtEG processes is calculated as shown in Fig. 10
(a)e(c). The TPC of the Tri-CtEG process is reduced from 716.38 to
613.99 $/t-EG because the TRM unit is integrated to reuse CO2 and
effectively produce syngas as shown in Fig. 9 (a). Moreover, the
operation and maintenance costs of the Tri-CtEG process are
greatly reduced because the processing capacity of the complicated
WGS, CG and AGR are greatly decreased. Additionally, the cost of
raw material (CR) is obviously reduced due to the low price of COG
and low consumption of raw material as shown in Fig. 9 (b) and (c).
Therefore, the proposed Tri-CtEG process is a cheaper method to
produce ethylene glycol than the CtEG process.

4.4.3. Effect of CO2 tax on return on investment


To further identify the advantages of the reduction of CO2
emission, the effect of CO2 tax on the economic performance of the
process is investigated and shown in Fig. 10. The return on in-
vestment of the CtEG and Tri-CtEG processes is about 8.5% and
13.7% without consideration of CO2 tax. However, when CO2 tax is Fig. 10. Effect of CO2 tax on the economic performance of the CtEG and Tri-CtEG
increased from zero to 50 $/t [45,46], the production cost of the processes.

CtEG and Tri-CtEG processes is increased by 23.2% and 7.2%. As a


result, the return on investment of the CtEG process is decreased
from 8.5% to 3.6%, and that of the Tri-CtEG process is decreased the CtEG and Tri-CtEG processes is conducted and indicated in
from 13.7% to 12.1%. Therefore, due to the less CO2 emission, the Fig. 11.
proposed Tri-CtEG process has a better economic performance and As Fig. 11 shown, the Tri-CtEG process has a better environ-
competitiveness than the conventional CtEG process. mental performance compared with the CtEG process since the
total CO2 emission of the Tri-CtEG process is only 0.89 t/t-EG, which
is 2.43 t/t-EG lower than the CtEG process, especially the direct CO2
4.5. Environmental performance
emission is reduced by 98.06%. Moreover, almost 94.38% of CO2
emission in the proposed process is generated by indirect CO2
In this study, both the direct and indirect CO2 emissions of these
emission and the direct CO2 emission from the process itself is only
two processes are considered to comprehensively compare their
0.05 t/t-EG. Most of the CO2 of the conventional process is reused in
environmental performance. The environmental performance of

Fig. 9. Comparison of the TPC of the CtEG and Tri-CtEG processes.

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Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

5. Conclusions

An integrated coal to ethylene glycol process with coke oven gas


tri-reforming technology (Tri-CtEG) is developed to reduce and
utilize the CO2 emission of the conventional coal to ethylene glycol
(CtEG) process. A meticulous simulation of the proposed process is
carried out to investigate and optimize the key operational pa-
rameters for optimal system performance. The technical, economic
and environmental performance of the Tri-CtEG process is analyzed
on the basis of the established models and simulation results. Thus,
the following conclusions can be obtained:

(1) The optimal COG/coal ratio of the Tri-CtEG process is


95 kmol/t. The optimal ratio among CH4, CO2, H2O and O2 of
the tri-reforming unit is 1: 1.43: 2.15: 0.44, and its temper-
ature is suggested to 850  C.
(2) The technical performance of the Tri-CtEG process is signif-
icantly better than that of the CtEG process since its carbon
and exergy efficiencies are 50.94% and 15.16% higher than
those of the CtEG process.
(3) The economic performance of the Tri-CtEG process is much
better than that of the CtEG process because its capital in-
Fig. 11. Environmental performance of the CtEG and Tri-CtEG processes. vestment and production cost are saved by 16.1% and 14.2%
in comparison to the CtEG process. Moreover, the return on
investment of the of the Tri-CtEG process is 5.2% higher than
the Tri-CtEG process. Hence, the environmental performance of the that of the CtEG process.
proposed Tri-CtEG process is greatly better than that of the con- (4) The proposed Tri-CtEG process effectively reduces the CO2
ventional process. emissions of the conventional CtEG process. The direct CO2
emission from the proposed process is only 0.05 t/t-EG,
which reduces 98.06% CO2 emission of the CtEG process.
4.6. Comprehensive evaluation
Thus, compared to the conventional CtEG process, the proposed
The comprehensive comparison of the performance of the CtEG process has excellent performance in carbon and exergy efficiency,
and Tri-CtEG processes are shown in Table 8. The proposed Tri-CtEG economic benefits as well as CO2 reduction. It is a promising
process shows significantly advantages in the aspect of carbon ef- method for the traditional CtEG industry to save energy and reduce
ficiency, exergy efficiency, ROI, and CO2 emission in comparison to carbon emissions.
the conventional CtEG process. The carbon and exergy efficiencies
of the proposed process are increased by 50.94% and 15.16%. The Author contributions
ROI of the proposed process is increased by 5.2% and 8.5% without
and with CO2 tax; while the total CO2 emission is reduced by Qingchun Yang: Conceptualization, Funding acquisition, Writing
73.19%. In particular, the direct CO2 emission is reduced by 98.06%. e review & editing, Simin Xu: Methodology, Investigation, Writing
Thus, the technical, economic and environmental performance of e original draft, Jinliang Zhang: Methodology, Investigation,
the Tri-CtEG process is much better than those of the CtEG process. Chenglin Liu: Software, Writing e original draft, Dawei Zhang:
Coal based chemical process integrated with tri-reforming tech- Methodology, Supervision, Project administration, Huairong Zhou:
nology is a promising direction to reduce and reuse its CO2 Visualization, Formal analysis, Writing e review & editing, Shumei
emissions. Mei: Resources, Writing e review & editing, Minglin Gao: Re-
sources, Formal analysis, Hongyan Liu: Data curation, Formal
analysis, Qingchun Yang: Conceptualization, Funding acquisition.
Table 8
Comprehensive comparison of the CtEG and Tri-CtEG processes.
Declaration of competing interest
Item CtEG process Tri-CtEG

Consumption The authors declare that they have no known competing


Coal input (t/t-EG) 2.55 0.56 financial interests or personal relationships that could have
COG input (kmol/t-EG) / 53.60 appeared to influence the work reported in this paper.
Oxygen consumption (t/t-EG) 1.68 0.76
Total utilities (MW/t-EG) 2.47 2.80
Economic cost Acknowledgements
Total capital cost ($/t-EG) 2552 2141
Total production cost ($/t-EG) 716.38 613.99 The authors are grateful for financial support from Natural Sci-
Performance comparison
ence Foundation of Anhui Province (No. 1908085QB69) and Post-
Carbon efficiency (%) 21.23 72.17
Exergy efficiency (%) 30.68 45.84
doctoral Research Station of Anhui HaoYuan Chemical Group Co.,
ROI without CO2 tax (%) 8.5 13.7 Ltd.
ROI with CO2 tax (50 $/t, %) 3.6 12.1
CO2 emission (t/t-EG) 3.32 0.89 Appendix A. Supplementary data

Supplementary data to this article can be found online at


12
Q. Yang, S. Xu, J. Zhang et al. Energy 229 (2021) 120713

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