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What is the best green propylene production

pathway?: technical, economic, and environmental
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Cite this: Green Chem., 2021, 23,

7635 assessment†
Heehyang Kim,‡a Boreum Lee,‡a Dongjun Lim,a Changgwon Choea and
Hankwon Lim *a,b

Received 20th May 2021,
Accepted 26th August 2021
DOI: 10.1039/d1gc01791h
rsc.li/greenchem
Owing to the increasing demand for propylene, many propylene production pathways have been devel-
oped, such as naphtha catalytic cracking, olefin metathesis, propane dehydrogenation, and methanol to
propylene (MTP) conversion. As environmental regulations become more stringent, green propylene should
be explored to enhance sustainable production and reduce CO2 emissions. MTP conversion through CO2
hydrogenation (indirect MeOH synthesis) and CO2 electrolysis (direct MeOH synthesis) has been explored as a
green propylene production pathway. To evaluate the possibility of green propylene production from techni-
cal, economic, and environmental perspectives, process simulation, economic analysis, and environmental
assessment were performed for MTP conversion via indirect and direct methanol synthesis. Furthermore, the
best alternative for green propylene production was determined via an analytic hierarchy process, considering
technical, economic, and environmental aspects, at the same time, with different weighted values of each cri-
terion, under uncertainty. Our results indicated that MTP via direct MeOH synthesis was superior in cases
where the environmental impact is the most important, while MTP via indirect MeOH synthesis was the most
appropriate alternative for green propylene production, with the technical and economic impacts being more
critical than the environmental impacts.

1. Introduction attracting attention due to the shale gas revolution as it uses

With the revolution of considerable shale gas extraction in the
United States (US), the chemical and petrochemical industries
underwent significant transitions until 2011.1,2 High-value pro-
ducts such as ethylene and propylene are traditionally pro-
duced from crude oil via the naphtha cracking center (NCC)
process, given the historical high price of natural gas.3,4 The
ethane cracking center (ECC) process uses ethane gas as a
feedstock to produce olefins and can utilize cheap shale
gas.5–7 However, the variety of products available for olefin pro-
duction in the ECC process is low, as ethylene accounts for
over 75% of ECC products.8 To continue meeting the disparity
in the demand and supply of propylene every year, olefin meta-
thesis and propane dehydrogenation reactions are being
developed.9–11 The methanol to olefins (MTO) process is also
a
School of Energy and Chemical Engineering, Ulsan National Institute of Science and
Technology, 50 UNIST-gil, Eonyang-eup, Ulju-gun, Ulsan 44919, Republic of Korea.
E-mail: hklim@unist.ac.kr; Tel: +82 52 217 2935
b
Department of Energy Engineering, Ulsan National Institute of Science and
Technology, 50 UNIST-gil, Eonyang-eup, Ulju-gun, Ulsan 44919, Republic of Korea
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
d1gc01791h
‡ Both authors contributed equally to this work.
the most methane in shale gas and transforms it into propy-
lene or ethylene.12,13 In particular, the global propylene
demand is expected to continue to rise owing to the low-cost
ethane from shale gas and strong demand for polypropylene
(PP) in emerging markets.14,15 Various propylene production
pathways, including fluid catalytic cracking (FCC), olefin meta-
thesis, propane dehydrogenation (PDH), and methanol to pro-
pylene (MTP) conversion, have been explored in previous
studies.16–18 Rodríguez-Vallejo et al.19 conducted techno-econ-
omic analysis, life-cycle assessment, and monetization for
various propylene production routes (coal-to-propylene,
natural gas-to-propylene, naphtha steam cracking, and
propane dehydrogenation) based on process simulation
results, and found that MTP routes could compete with con-
ventional steam cracking of naphtha and propane dehydro-
genation, however, the environmental aspects process must be
developed for green propylene production. Jasper and El-
Halwagi20 compared the MTO and MTP processes considering
different feedstocks, such as methanol (MeOH) or natural gas,
through techno-economic analysis and environmental assess-
ment, and the results, showed that the commercial MeOH
market price is lower than the cost of MeOH production from
natural gas for MTO and MTP, and the MTP process released
less CO2 than the MTO process. Zhao et al.21 conducted a com-

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Paper
prehensive economic analysis of 20 light-olefin production
pathways considering various resources such as petroleum,
coal, natural gas, biomass, and CO2. Propylene production
from renewable pathways is not currently economically com-
petitive, according to the trend of the total production costs,
and the cost-competitiveness of the process should be
improved by reducing the feedstock cost and technological
development. Rosental et al.22 conducted life-cycle impact
assessment, including global warming impact, cumulated
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energy demand, acidification potential, eutrophication poten-
tial, ozone depletion potential, and particulate matter for-
mation on a cradle-to-gate basis for the production of various
organic chemicals, such as MeOH, ethylene, propylene,
benzene, toluene, and mixed xylenes, using the following
technologies: hydrogen production from alkaline water electro-
lysis coupled with CO2 captured from industrial sources;
MeOH synthesis; MTO; and MeOH to aromatics synthesis,
including aromatics separation. The global warming impact
value was 50 to 540 kg-CO2eq. per tonproduct, while that of pro-
duction from fossil fuels was 2002 to 4648 kg-CO2eq. per ton-
23
product. Gao et al. conducted a life-cycle assessment for coal-
based MTO processes to control energy and water conserva-
tion, and CO2/SO2/NOx emissions by dividing the process into
six sub-processes, including mining, transportation, coal to
MeOH, MTO, olefin delivery, and CO2 capture and storage.
According to their results, the coal to MeOH process accounted
for 71.04% of energy consumption in the coal-based MTO
process. Many studies have been conducted on propylene pro-
duction, however, few have simultaneously covered techno-
economic and environmental assessments of propylene pro-
duction via various pathways, including renewable sources.
Therefore, in this work, techno-economic and environmental
assessments were performed for green propylene production
pathway to evaluate the feasibility in terms of technical, econ-
omic, and environmental perspectives, simultaneously.
Moreover, priority analysis through an analytic hierarchy
process, which is a multi-criteria decision analysis method to
determine the best alternative for the proposed process with
different weighted values for each criterion, has been con-
ducted to determine the most appropriate pathway for green
Fig. 1 Schematic diagram of the green propylene production process via indirect and direct MeOH synthesis.
7636 | Green Chem., 2021, 23, 7635–7645
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propylene production according to different weighted values of
the technical, economic, and environmental impacts because
three parameters should be considered to commercialize MTP
process, at the same time. In this work, propylene production
via the MTP process through CO2 hydrogenation (indirect
MeOH synthesis) and CO2 electrolysis (direct MeOH synthesis)
with surplus renewable electricity was identified as a green
process, because a lot of CO2 is emitted during MTP pro-
duction: MTP from natural gas (16.4 kg-CO2eq. per kg-propy-
lene), MTP from coal (4.3 kg-CO2eq. per kg-propylene),
propane dehydrogenation (2.2 kg-CO2eq. per kg-propylene),
and naphtha cracking (1.6 kg-CO2eq. per kg-propylene).19
Fig. 1 presents an overall schematic diagram of green propy-
lene production from MTP, including the indirect and direct
MeOH production pathways.
Steam methane reforming (SMR) and coal gasification (CG)
are usually used for indirect MeOH production, which consists
of the CO and CO2 hydrogenation, and reverse water gas shift
(RWGS) reactions, resulting in significant CO2 emissions.24–26
However, power to H2, where green H2 is produced by water
electrolysis using electricity generated from renewable energy
sources, has received much attention as it can store surplus
electricity due to the disparity between energy demand and
supply caused by its intermittent nature. Therefore, the use of
green H2 produced by power to H2 can aid in MeOH production
with low CO2 emissions.27,28 CO2 electrolysis is used for direct
MeOH production, which is also a carbon-neutral pathway.29,30
This work conducts a comprehensive analysis, including techni-
cal, economic, and environmental aspects, simultaneously, of the
green propylene production process via indirect and direct MeOH
synthesis based on process modeling using Aspen Plus®, which
is a commercial process simulation program. Economic analysis
of green propylene production via indirect and direct MeOH syn-
thesis methods was also conducted to compare the unit propy-
lene production cost with that of the conventional propylene pro-
duction process. Additionally, environmental assessment was con-
ducted using GREET®, which simulates the energy use and emis-
sions of greenhouse gases, followed by fuel consumption and
transportation. Ultimately, green propylene production routes
could then be suggested based on technical, economic, and
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environmental aspects, using techno-economic analysis, environ- R6 : 2MeOH ! C2 H4 þ 2H2 O ð6Þ

mental assessment, and analytic hierarchy process (AHP).
R7 : C2 H4 þ DME ! C3 H6 þ MeOH ð7Þ

2. Methods R8 : C3 H6 þ DME ! C4 H8 þ MeOH ð8Þ

2.1. Process modeling
R9 : C4 H8 þ DME ! C5 H10 þ MeOH ð9Þ
Fig. 2 shows the process flow diagram (PFD) of MeOH pro-
duction and MTP based on the process developed in the R10 : MeOH ! CO þ 2H2 ð10Þ
literature.31,32
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The main flow results for green propylene production R11 : CO þ H2 O ! CO2 þ H2 ð11Þ
process modeling, including MeOH synthesis and MTP, are
provided in the ESI (Table S1†). MeOH is produced by the R12 : MeOH þ H2 ! CH4 þ H2 O ð12Þ
hydrogenation of CO2 (R1), RWGS reaction (R2), and CO hydro-
R13 : C2 H4 þ H2 ! C2 H6 ð13Þ
genation (R3), according to eqn (1)–(3).

R1 : CO2 þ 3H2 ! CH3 OH þ H2 O ð1Þ
R2 : CO2 þ H2 ! CO þ H2 O ð2Þ
R3 : CO þ 2H2 ! CH3 OH ð3Þ
MeOH can be converted into various hydrocarbons, such as
methane, ethylene, propylene, butene, and pentene, after
going through the reaction steps. All reaction networks for the
MTO process include the dehydration of MeOH, a consecutive
synthesis reaction to produce olefins, hydrogenation of
alkenes, decomposition of MeOH to CO, and water gas shift
reaction, as shown in eqn (4)–(13):
R4 : 2MeOH $ ½ðCH3 Þ2 O þ H2 O ð4Þ
R5 : 2½ðCH3 Þ2 O ! C2 H4 þ 2MeOH ð5Þ
Based on these reactions, the experimental kinetics over
Cu/ZnO/Al2O3 and SAPO-34 catalysts, were utilized for the
MeOH and MTP reactors, respectively.32,33 The equilibrium
constant (Kp) of the reaction was calculated from the experi-
mental relationship over the ZSM-5 catalyst for the MTP
process according to Gayubo et al.,34 as follows:
ΔG
R ln Kp ¼
T
4163
¼ þ 2 ln T  1:01  103 T  5:82  106 T 2
T
 10:76
ð14Þ
The pre-exponent and activation energies in the reaction
rate equation are listed in Table 1.32,33

Fig. 2 Process flow diagram (PFD) for green propylene production process via CO2 hydrogenation.

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Paper Green Chemistry

Table 1 Reaction rate equation for MeOH synthesis and MTP process

MeOH synthesis

Parameters of the kinetic model

Reaction
Bi
ln ki ¼ Ai þ
T
k1 A1 −29.87
B1 4811.2
k2 A2 8.147
2   B2 0
k1 PCO2 PH2  k6 PH2 O PCH3 OH PH kmol
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r1 ¼  3
2
k3 A3 −6.452
1 þ k P 0:5 þ k P
1 þ k2 PH2 O PH kgcat s
2 3 H2 4 H2 O B3 2068.4
k4 A4 −34.95
1   B4 14 928.9
k5 PCO2  k7 PH2 O PCO PH kmol
r2 ¼  1 þ k P 0:5 þ k P
2
 k5 A5 4.804
1 þ k2 PH2 O PH2 3 H2 4 H2 O kgcat s B5 −11 797.5
k6 A6 17.55
B6 −2249.8
k7 A7 0.1310
B7 −7023.5

MTP process
 m3 ðm3 Þ
2  kJ
k0j j ¼ 2; 3 k0j ¼ for other k0j ¼ Ej Ej ¼
Reaction gh g mol h mol
k01
r3 ¼ k01 PMeOH
2
 PDME PH2 O 5.7 × 105 87.1
r4 = k02PDME K 1.7 × 106 76.9
r5 = k03PMeOH 1.9 × 106 112.5
r6 = k04PDMEPC2H4 3.7 × 105 64.5
r7 = k05PDMEPC3H6 2.7 × 106 82.2
r8 = k06PDMEPC4H8 2.06 × 106 83.4
r9 = k07PMeOH 1.6 × 106 113.3
r10 = k08PCOPH2O 2 × 106 119
r11 = k09PMeOHPH2 1 × 106 97
r12 = k010PC2H4PH2 1.3 × 106 110.3

2.2. Economic analysis mation, and the chemical engineering plant cost index (CEPCI),
Economic analysis of green propylene production was conducted which is used to reflect the change in value over time, were con-
to calculate the unit propylene production cost based on econ- sidered to estimate the effect of the equipment capacity and time
omic data from previous studies and the economic analysis on the purchased equipment cost, as shown in eqn (15).
methods of Turton et al.35 To calculate the unit propylene pro-
n

Aa Ia
duction cost, itemized cost estimation was first conducted by clas- Capital investment ¼ reference cost   ð15Þ
Ab Ib
sifying costs into capital expenditures (CAPEX) and operating
expenditures (OPEX). For green propylene production via indirect where A is an attribution of equipment such as the feed flow
MeOH production, the MeOH synthesis reactor, compressor, flash rate, power, and production capacity, n is the cost exponent,
drum, MeOH distillation, MTO reactor, propylene distillation, and I is the CEPCI.
heat exchanger, and supplement are classified as CAPEX, and the In this work, the cost exponents for the MeOH distilla-
reactants, such as H2 and CO2, labor, maintenance, and other tion,37 MTO reactor,38 and propylene distillation39 were 0.7,
costs are regarded as OPEX. For MTP via direct MeOH synthesis, 0.6, and 0.64, respectively, and the items involved in MTP via
the electrolyzer, balance of plant, distillation, pressure swing indirect MeOH synthesis were calculated using cost functions
adsorption (PSA), MTO reactor, propylene distillation, and sup- based on base price, as described by eqn (16)–(18).40–42
plement are categorized as CAPEX, while the distillation operating
MeOH reactor ¼ 7106:85  ðM in Þ0:7 ð16Þ
cost, PSA operating cost, CO2 cost, water cost, maintenance, labor,
and other costs are regarded as OPEX. Surplus renewable electri- !0:82
Wcomp
city generated due to the disparity between energy demand and Compressor cost ¼ 8650  ð17Þ
ηcomp
supply caused by the intermittent nature of renewable energy36
was utilized for both green propylene production methods.
Flash drum ¼ 2:47  9:832  ðF gas Þ0:8 ð18Þ
2.2.1. Economic analysis of propylene production via indir-
ect MeOH synthesis. In this work, the six-tenths rule, which where Min is the MeOH synthesis feed rate (kg h−1), Wcomp is
uses a cost exponent of 0.6 for equipment with limited cost infor- the compressor power (hp), ηcomp is the compressor

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efficiency (%), and Fgas is the feed rate (kg s−1) in the flash
drum.
The supplement cost was assumed to be 20% of the total
main equipment costs. The annual capital costs were calcu-
lated by considering the capital recovery factor (CRF),
(eqn (19)), which is defined as the annuity factor:
ið1 þ iÞn
Capital recovery factorðCRFÞ ¼
ð1 þ iÞn  1
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where i is the discounted rate and n is the project period.
The operating costs included the reactant (H2 and CO2),
labor, maintenance, and other costs. For MTP via indirect MeOH
synthesis, the renewable H2 cost according to a regression
method with surplus electricity,43–46 CO2 capture cost of 74 $ per
ton,47,48 and CO2 credit of 29.6 $ per ton (ref. 49) were con-
sidered. The reactant cost was calculated according to the H2 and
CO2 input flow rates based on the process simulation results,
and the reactant costs could be calculated using eqn (20):
Reactants cost ¼ H2 cost  input rateH2  M:W: H2
þ input rateCO2  M:W: CO2  ðcapture costCO2  CO2 creditÞ
where M.W. is the molecular weight, and CO2 credit is the CO2
allowance price.
The regression method for H2 cost considered several unit
H2 production costs according to the H2 production capacity
reported in the literature,43–46 and the equation of H2 cost
using regression method was calculated by eqn (21):
H2 cost ¼ 1:758  H2 flowrate0:7052 þ 1:628
The labor cost was assumed to be 0.3% of the total main
equipment costs,50 while the maintenance and other costs were
assumed to constitute 2% and 1% of the total initial capital cost,
respectively, to cover the costs of process water, catalysts, utilities,
and so on. Additionally, the unit propylene production cost was
obtained by dividing the total annual cost ($ per y) by the annual
propylene production capacity (kg per y).
2.2.2. Economic analysis of propylene production via
direct MeOH synthesis. For MTP via direct MeOH synthesis,
the detailed itemized cost estimation methods for direct
MeOH synthesis proposed by Jouny et al.51 were followed in
this study, and other estimations were conducted in the same
manner. The capital cost for the electrolyzer was estimated
based on the cost function, as follows (eqn (22)):
Electrolyzer cost ¼ reference of electrolyzer cost
total current
 ð22Þ
current density
The reference values for the electrolyzer cost and current
density were 1840 $ per m2 and 0.2 A cm−2, respectively. The
balance of plant, distillation cost, and PSA cost were calculated
using cost functions, as described by eqn (23)–(25).
0:35
Balance of plant ¼ electrolyzer cost 
0:65
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electrolyte flow rate 0:7
Distillation cost ¼ reference cost 
1000
ð24Þ

0:7
total gas flow
PSA ¼ reference cost  ð25Þ
1000
The supplement cost was assumed to be 20% of the sum of
ð19Þ
the main equipment costs. The distillation operating cost and
PSA operating cost were estimated by scaling up the reference
costs according to the flow rates, as shown in eqn (26) and
(27).
Distillation operating cost ¼ reference cost
electrolyte flow rate
 ð26Þ
1000
PSA operating cost ¼ reference cost  total gas flow
 electricity price ð27Þ
For MTP via direct MeOH synthesis, the other items were
calculated following the same methods used for MTP via indir-
ð20Þ ect MeOH synthesis.
2.3. Environmental impact assessment
Environmental impact assessment was conducted by applying
life-cycle assessment, which is a well-established holistic
method by considering all processes from raw material acqui-
sition through production, use, and end-of-life treatment.52,53
The GREET® database from the Argonne National Laboratory
ð21Þ was used to evaluate the energy use and emission outputs of
vehicles and fuel combinations normally. The chemical
process can also be covered by the GREET® database based on
reference information related to H2 production for H2 fuel cell
electric vehicles, including naphtha cracking, steam methane
reforming, electrolysis, and coke oven gas purification.54 In the
environmental impact assessment, the functional unit for pro-
pylene was 1 ton of propylene produced. The GREET® data-
base was adapted based on process simulation results to
provide environmental impact data for MTP via direct and
indirect MeOH synthesis, and a gate-to-gate system boundary
was used for the environmental impact assessment of green
propylene production, as shown in Fig. S1 and S2.† The CO2
and GHG emissions associated with MTP via indirect and
direct MeOH synthesis were evaluated based on MeOH syn-
thesis and MTP processes.
2.4. Analytic hierarchy process
The analytic hierarchy process (AHP), developed by Thomas L.
Saaty,55 was performed to drive the best alternative for the
green propylene process, in terms of technical, economic, and
environmental aspects, simultaneously. Here, there are five
steps in the AHP: (1) goal definition, (2) construction of the
first-hierarchy with regard to technology readiness level (TRL),
unit propylene cost, and CO2 emissions, for MTP via indirect
ð23Þ
and direct MeOH synthesis, in terms of technical, economic,
Green Chem., 2021, 23, 7635–7645 | 7639

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and environmental aspects, respectively, (3) pairwise compari-
son for 1000 cases with different weighted values for technical,
economic, and environmental aspects, respectively, (4) priority
calculation, and (5) decision-making. The total weighted value
for 1 case was 1, meaning that the sum of the different
weighted values for the technical, economic, and environ-
mental criteria was one, and 1000 random numbers were gen-
erated as weighted values for each criterion. Fig. 3 shows the
frequency of the weighted values for technical, economic, and
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environmental criteria in this work, respectively.
3. Results and discussion
3.1. Optimization of operating conditions
To develop the green propylene production process simulation,
the operating conditions, including temperature and pressure,
were first optimized. The green propylene production process,
which combined MeOH synthesis and the MTP process, was
simulated based on the studies by Van-Dal et al.33 and
Najafabadi et al.,32 respectively. Fig. 4 shows the optimization
of the operating conditions based on the propylene yield, with
reaction temperatures ranging from 250 to 500 °C and press-
ures ranging from 1 to 12 bar.
The optimum propylene yield was achieved with a higher
mass flow rate at a temperature of 420 °C and pressure of 7
bar. Under the optimal operating conditions, the propylene
mole fraction was 33%, which is comparable to the experi-
mental results reported by Jiang et al.56
3.2. Economic analysis
An economic analysis of green propylene production was con-
ducted for MTP via indirect and direct MeOH synthesis under
the optimal operating conditions of 420 °C and 7 bar based on
the process simulation results. For MTP via direct MeOH syn-
thesis, direct MeOH synthesis based on the CO2 electrolysis
Fig. 3 Frequency of weighted values for the technical, economic, and
environmental criteria.
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Fig. 4 Optimization of the operating conditions for propylene pro-
duction via indirect MeOH synthesis based on process simulation.
process was considered to be the economic component, based
on the literature.51 An economic analysis was carried out to
estimate the unit propylene production cost for MTP via indir-
ect and direct MeOH synthesis for propylene production
capacities of 50 and 100 ton per d, as shown in Fig. 5.
The cost of MTP via indirect MeOH synthesis was lower
than that of MTP via direct MeOH synthesis. At a propylene
production capacity of 50 ton per d, the cost of MTP via indir-
ect MeOH synthesis (3.44 $ per kg) was lower than that of MTP
via direct MeOH synthesis (4.33 $ per kg), with a cost saving of
25.87%. It is noteworthy that the reactants (H2 and CO2)
accounted for a dominant proportion (79.58% and 83.01% at
50 and 100 ton per d, respectively) of the itemized unit propy-
lene production cost of MTP via indirect MeOH synthesis, and
significantly affected the unit propylene production cost with
increases in the propylene production capacity. The costs of
the CO2 reactant and electrolyzer were prominent factors in
the cost of MTP via direct MeOH synthesis (20.14% and
20.69% for the CO2 reactant at 50 and 100 ton per d, respect-
ively). The commercialized MTP process developed by Lurgi in
Air Liquide has produced a full-size MTP plant capacity of 500
ton per d,57 and the unit propylene production costs for MTP
via indirect and direct MeOH synthesis were determined for
propylene production capacities of 50, 100, 300, and 500 ton
per d, as shown in Fig. 6.
These results indicate that the unit propylene production
cost can fluctuate according to the propylene production
capacity. In particular, the unit propylene production cost of
both MTP pathways could be decreased by increasing the pro-
pylene production capacity, and included reactants as a domi-
nant factor. The detailed CAPEX and OPEX percentages of
MTP via indirect MeOH synthesis were 15%, 13%, 9%, and 7%
and 85%, 87%, 91%, and 93% for propylene production
capacities of 50, 100, 300, and 500 ton per d, respectively,
while those of MTP via direct MeOH synthesis were 50%, 49%,
48%, and 48% and 50%, 51%, 52%, and 52%, respectively. For
both MTP pathways, the percentage of CAPEX decreased with
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Fig. 5 Itemized propylene production costs for MTP via indirect and
direct MeOH synthesis.
the propylene production capacity due to economies of scale.
Predictive cost analysis was conducted based on the cost func-
tion for green propylene production via indirect and direct
Fig. 6 Scaled-up simulated green propylene production via indirect and direct MeOH synthesis.
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MeOH synthesis, which was estimated using regression ana-
lysis as shown in Fig. 7.
Respective cost functions of f (x) = 3.444 × x−0.4034 + 2.682 ($
per kg) and f (x) = 9.3324 × x−0.1093 − 1.835 ($ per kg) were
obtained for green propylene production via indirect and
direct MeOH synthesis. Fig. 7a shows the gradually declining
unit propylene production cost due to the higher OPEX of
MTP via indirect MeOH synthesis. However, the unit propylene
production cost of MTP via indirect MeOH synthesis is still
not comparable with that of conventional MTP production
from natural gas. Therefore, approaches to reducing the reac-
tants (green H2 and CO2) for green propylene production
should be investigated. However, Fig. 7b indicates that the
unit propylene production cost could be reduced by an
economy of scale and a relatively lower percentage of OPEX.
Additionally, the unit propylene production cost of MTP via
direct MeOH synthesis could compete with that of convention-
al MTP production from natural gas for a propylene pro-
duction capacity of over 5000 tons per d. Therefore, further
research for the reduction of the unit propylene production
cost is required to develop green propylene production via
direct MeOH synthesis.
3.3. Environmental impact assessment
Fig. 8 presents the environmental impacts, including the CO2
and GHG emissions of propylene production via indirect and
direct MeOH synthesis at a produced propylene flow rate of 1
ton per d.
Overall, the CO2 and GHG emissions were very similar, and
MTP via indirect MeOH synthesis was absolutely higher than
MTP via direct MeOH synthesis. For MTP via indirect MeOH
synthesis, the CO2 and GHG emissions were 54% and 46%
(923.73 kg-CO2eq. per ton-propylene and 987.22 kg-CO2eq. per
ton-propylene) for the MeOH synthesis and MTP processes,
respectively. For MTP via direct MeOH synthesis, the MeOH
synthesis process with CO2 electrolysis was considered, which
a green MeOH synthesis method, and 100% of the CO2 and
GHG emissions (427.58 kg-CO2eq. per ton-propylene and
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Fig. 7 Cost equations for green propylene production via (a) indirect MeOH synthesis and (b) direct MeOH synthesis.

Fig. 8 Environmental impacts of green propylene production via indirect and direct MeOH synthesis.

453.34 kg-CO2eq. per ton-propylene, respectively) originated

from the MTP process. Reasonable environmental results were
achieved for green propylene production via indirect and
direct MeOH synthesis when compared to MTP from natural
gas (16.4 kg-CO2eq. per kg-propylene), MTP from coal (4.3 kg-
CO2eq. per kg-propylene), propane dehydrogenation (2.2 kg-
CO2eq. per kg-propylene), and naphtha cracking (1.6 kg-
CO2eq. per kg-propylene).19 The much greater environmental
impact of the MTP via direct MeOH synthesis indicates that it
is a superior option for green propylene production in terms
of the environmental aspect.

3.4. Analytic hierarchy process

Fig. 9 shows the results of the uncertainty analysis of the AHP
for green propylene production via indirect and direct MeOH
synthesis under 1000 cases with different weighted values for
technical, economic, and environmental aspects, respectively.
The priority for MTP via indirect MeOH synthesis was dis-
tributed at a higher position than that of MTP via the direct
MeOH synthesis. Fig. 10 presents the AHP results for 10 of the
1000 cases covered in this work, in terms of the weighted Fig. 9 Uncertainty analysis of the analytic hierarchy process (AHP)
values for the technical, economic, and environmental criteria, methodology for green propylene production via indirect and direct
as well as the priority for each case. MeOH synthesis.

7642 | Green Chem., 2021, 23, 7635–7645 This journal is © The Royal Society of Chemistry 2021
 View Article Online

Green Chemistry Paper

synthesis processes were considered based on CO2 hydrogen-

ation and CO2 electrolysis, respectively.
Techno-economic analysis was conducted to estimate the
unit propylene production cost for green propylene production
via indirect and direct MeOH synthesis using economic func-
tions based on the process simulation results such as the opti-
mized operating conditions for MTP via indirect MeOH syn-
thesis process modeling. The techno-economic analysis results
indicated that the reactant is a key economic factor of propy-
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lene production affecting the unit propylene production cost,

and the respective costs of 2.95 $ per kg and 2.89 $ per kg were
calculated for the propylene production capacity of 500 ton per
d (industrial capacity) for MTP via indirect and direct MeOH
synthesis, respectively. Further, an environmental assessment
was conducted to calculate the CO2 and GHG emissions in
Fig. 10 AHP results for the 10 selected cases in terms of the weighted order to suggest a more sustainable propylene production
values as well as priority. method. The CO2 emissions for green propylene production
were 927.73 kg-CO2eq. per ton-propylene and 427.58 kg-CO2eq.
per ton-propylene, thus, it was superior to the other propylene
Here, higher priority calculated from the technical, econ- production pathways. Based on the technical, economic, and
omic, and environmental results with different weighted environmental assessment results, the most appropriate
values indicates, a better alternative. The results indicate that pathway for green propylene production was determined with
MTP via indirect MeOH synthesis was the most suitable different weighted values of technology readiness level (TRL),
technology for green propylene production when the weighted unit propylene production, and CO2 emission values via the
value of the technical criterion was higher (Trial 4). analytic hierarchy process (AHP). The AHP results, indicate
Additionally, MTP via indirect MeOH synthesis was the best that MTP via indirect MeOH synthesis was the best approach
option when the weighted values for the criteria decreased in when weighting technical and economic factors higher than
the following order: economic, environmental, and technical environmental factors, while MTP via direct MeOH synthesis
(Trial 2). MTP via indirect MeOH synthesis was also the best was superior when focusing on the environmental impact.
option when considering Trial 7 (i.e., the technical criterion Consequently, two pathways, i.e., MTP via direct or indirect
was weighted higher than the environmental criterion, with MeOH synthesis, were introduced for green propylene pro-
the economic criterion weighted highest). If the environmental duction in this work, as clean and sustainable propylene pro-
criterion was the most important (Trials 3 and 8), MTP via duction should be necessary to address the global environ-
direct MeOH synthesis was the most suitable alternative for mental issue (i.e., global warming). It is beneficial to deter-
propylene production. Furthermore, MTP via indirect MeOH mine the best process when considering different weighted
synthesis had a relatively higher priority than MTP via direct values of technical, economic, and environmental factors
MeOH synthesis; in Trial 9, in which the weighted values of according to the AHP results based on techno-economic ana-
technical and environmental criteria were similar, and the lysis and the environmental impact analysis results.
economic criterion was relatively unimportant. Therefore, the
best green propylene production methods will differ according
to the weighted values of technical, economic, and environ-
Abbreviations
mental criteria, according to the comprehensive AHP results.
US United States
NCC Naphtha cracking center
4. Conclusions ECC Ethane cracking center
MTO Methanol to olefins
As the global propylene demand has increased due to an PP Polypropylene
imbalance between ethylene and propylene, with the low cost FCC Fluid catalytic cracking
of ethane and high demand for polypropylene, as well as PDH Propane dehydrogenation
environmental issues that have received increasing attention, a MTP Methanol to propylene
comprehensive analysis simultaneously considering technical, MeOH Methanol
economic, and environmental aspects, at the same time, must SMR Steam methane reforming
be conducted. In this work, green propylene production by CG Coal gasification
methanol to propylene (MTP) via indirect and direct methanol RWGS Reverse water gas shift
(MeOH) synthesis was explored. To assess renewable MeOH AHP Analytic hierarchy process
synthesis processes in detail, the indirect and direct MeOH TRL Technology readiness level

This journal is © The Royal Society of Chemistry 2021 Green Chem., 2021, 23, 7635–7645 | 7643

Paper
PFD Process flow diagram
CAPEX Capital expenditures
OPEX Operating expenditures
PSA Pressure swing adsorption
CEPCI Chemical engineering plant cost index
CRF Capital recovery factor
Author contributions
Published on 08 September 2021. Downloaded by EKB Data Center on 11/30/2023 4:42:28 PM.
Heehyang Kim: Writing – original draft, conceptualization,
methodology, investigation. Boreum Lee: Data curation,
writing – original draft. Dongjun Lim: Methodology, formal
analysis. Changgwon Choe: Validation. Hankwon Lim:
Conceptualization, writing – review & editing, supervision,
project administration.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This research was supported by the Hydrogen Energy
Innovation Technology Development Program of the National
Research Foundation of Korea (NRF) funded by the Korean
government (Ministry of Science and ICT (MSIT))
(NRF-2019M3E6A1064290) and also supported by the National
Research Foundation of Korea (NRF) grant funded by the
Korea government (NRF-2019M1A2A2065614).
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