Fuel xxx (2016) xxx–xxx

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Full Length Article

Carbon dioxide utilization in a gas-to-methanol process combined with

CO2/Steam-mixed reforming: Techno-economic analysis
Chundong Zhang a, Ki-Won Jun a,⇑, Ruxing Gao b,c, Geunjae Kwak a, Hae-Gu Park a
a
C1 Gas Conversion Research Group, Carbon Resources Institute, Korea Research Institute of Chemical Technology (KRICT), Yuseong, Daejeon 34114, Republic of Korea
b
Korea Atomic Energy Research Institute, Yuseong, Daejeon 305-353, Republic of Korea
c
Quantum Energy Chemical Engineering, School of Engineering, Korea University of Science and Technology (UST), Yuseong, Daejeon 34113, Republic of Korea

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Two options of CO2 utilized gas-to-

methanol (CGTM) process are
proposed.

CO2 is converted via CO2/Steam-
mixed reforming and CO2
hydrogenation.

Process simulation and conceptual
design are implemented using Aspen
Plus.

Techno-economic analysis is
implemented to evaluate the
economic feasibility.

Both options are economically
feasible in the plant scale range of
2500–5000 TPD.

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

Article history: Conceptual design for two options of carbon-dioxide-utilized gas-to-methanol process (CGTM) was
Received 12 July 2016 implemented by using process simulation software Aspen Plus. The overall mass and energy stream
Received in revised form 26 September results as well as the thermal and carbon efficiency were obtained from the developed process models.
2016
Before the following economic evaluation and sensitivity analysis, total capital investment (TCI) and total
Accepted 2 November 2016
Available online xxxx
product cost (TPC) of both CGTM options were determined. Then, economic evaluation were conducted to
assess the economic profitability of the base cases for both CGTM options, using the economic evaluation
indicators such as net present value (NPV), internal rate of return (IRR), and discounted payback period
Keywords:
Greenhouse gas
(DPBP). Furthermore, sensitivity analysis as well as break-even analysis were also applied to investigate
CO2 utilization the economic performance of both CGTM options under different circumstances, by changing parameters
Gas-to-methanol such as methanol and NG prices, plant scale, and carbon tax. It was shown that the methanol price,
Methanol synthesis CAPEX, and NG price are the most sensitive factors, and the two CGTM options were economically feasi-
Economic analysis ble in the plant scale range of 2500–5000 ton per day, according to the economic evaluation indicators
NPV, IRR, and DPBP, and were more economically competitive in the case of higher plant scale and carbon
tax.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction

The increasing atmospheric CO2 levels and the depleting fossil

⇑ Corresponding author.
fuel reserves are regarded as the two major energy-related
E-mail address: kwjun@krict.re.kr (K.-W. Jun).

http://dx.doi.org/10.1016/j.fuel.2016.11.008
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Zhang C et al. Carbon dioxide utilization in a gas-to-methanol process combined with CO2/Steam-mixed reforming:
Techno-economic analysis. Fuel (2016), http://dx.doi.org/10.1016/j.fuel.2016.11.008
2 C. Zhang et al. / Fuel xxx (2016) xxx–xxx
problems facing us in the next 50 years [1]. One strategy to simul-
taneously address the above two problems is the utilization of CO2
as a carbon source for the synthesis of liquid fuels and/or petro-
chemicals [2,3]. In recent years, extensive efforts have been made
to develop efficient CO2 utilization technologies, among which
CO2 reforming and CO2 hydrogenation have been regarded as more
attractive methods for CO2 conversion [4–6]. It is because of their
capability to be applied in the gas-to-liquids (GTL) and gas-to-
methanol (GTM) processes on a large scale [7]. For instance, CO2
reforming can be combined with steam reforming which is widely
employed for syngas generation in the current natural gas (NG)
industry [8]. In addition, CO2 hydrogenation can be applied
together with CO hydrogenation for the synthesis of various chem-
icals and/or fuels such as hydrocarbons [9,10], DME [11], and
methanol [12].
Methanol is an important primary raw material for the energy
and chemical industries, because of its wide applications ranging
from energy uses (e.g., as a fuel by itself, or to be blended with
gasoline) to chemical uses (e.g., as a solvent, or to be converted
to formaldehyde, olefins, acetic acid, esters, etc.) [13,14]. Mean-
while, GTM process has gained extensive attentions since the past
decade due to the increasing trend in methanol demand as well as
the availability of abundant and cheap NG [15]. Besides, it will
attract more attentions in the coming years, owing to the extre-
mely abundant unconventional NG resources such as shale gas
and coal-bed methane, which are recently being exploited and uti-
lized [16,17]. Generally, a GTM process consists of three main
steps: (1) syngas generation via methane reforming technologies
such as auto-thermal reforming (ATR) [18], steam reforming of
methane (SRM) [19], partial oxidation of methane (POM) [20],
and carbon dioxide reforming of methane (CDM) [21]; (2) syngas
conversion through methanol synthesis technology, which pro-
duces crude methanol as well as few byproducts (e.g., ethanol
and DME) [13,22]; (3) methanol purification via distillation to pro-
duce purified methanol with required purity. Among the methane
reforming technologies mentioned above, none of them produces
syngas with suitable H2/(2CO + 3CO2) ratio, as can be directly sent
to the following methanol synthesis unit [5]. Hence, the additional
syngas ratio conditioning units are necessary. In addition, the ATR
and POM technologies need expensive air separation units to gen-
erate pure oxygen, which are associated with challenging safety
concerns because of the usage of pure oxygen [23]. However, the
combination of SRM and CDM, named CO2/Steam-mixed reforming
hereafter, can produce the syngas with flexible H2/(2CO + 3CO2)
ratios via controlling the two competitive methane reforming reac-
tions SRM and CDM. Thus, no additional syngas ratio conditioning
units are necessary in the case of CO2/Steam-mixed reforming,
which could save capital expenditures (CAPEX) and operating
expenditures (OPEX) of the GTM process. Meanwhile, CO2 can be
converted in both the reforming and methanol synthesis units to
produce final product methanol, which reduces the CO2 emissions
of the GTM process.
Therefore, based on the above considerations and our previous
technical study on the CO2 utilized GTM process (CGTM) [24], in
the present work, we mainly focused on the techno-economic
analysis for the two proposed CGTM options. During the economic
analysis, several economic evaluation indicators such as net pre-
sent value (NPV), internal rate of return (IRR), and discounted pay-
back period (DPBP) were determined for the base cases of both
proposed CGTM options. Besides, the effects of several factors, such
as methanol price, plant scale, NG price, and carbon tax were fur-
ther investigated in detail. It was shown that the two CGTM
options were economically feasible in the plant scale range of
2500–5000 ton per day (TPD), according to the evaluation indica-
tors NPV, IRR, and DPBP, and were more economically competitive
in the case of higher plant scale and carbon tax.
Please cite this article in press as: Zhang C et al. Carbon dioxide utilization in a gas-to-methanol process combined with CO2/Steam-mixed reforming:
Techno-economic analysis. Fuel (2016), http://dx.doi.org/10.1016/j.fuel.2016.11.008
2. Material and methods
2.1. Process modeling
Generally, a GTM process is usually comprised of several units:
units for feeding, gas pretreatment, reforming, methanol synthesis,
and methanol purification. However, in this work, the gas pretreat-
ment and methanol purification units were not investigated in
detail since they are already well established in the current NG
industry and their effects on the performance of the whole CGTM
process is relatively small, as also described in our previous study
[3,7,23,24]. Therefore, two simplified but meaningful CGTM
options were instead proposed, mainly focusing on the feeding,
reforming, methanol synthesis and recycling units combined with
several separation units, as illustrated in Fig. 1 [24]. Here, the main
difference between the two CGTM options is the feeding method of
the fresh feed CO2. More specifically, in option 1, fresh CO2 was fed
to the reforming unit to produce syngas via CO2/Steam-mixed
reforming first, and then to the methanol synthesis unit to produce
methanol via hydrogenation of CO2 and CO. While, in option 2,
fresh CO2 was fed to the methanol synthesis unit directly to pro-
duce methanol without entering into the reforming unit.
The criteria as well as some important assumptions applied in
the process models are outlined as follows: methane, ethane, pro-
pane, butane, CO2, and nitrogen were selected as the main compo-
nents in the fresh and fuel NG, and its typical composition is shown
in Table S1 of the Supplementary Information (SI). In both estab-
lished process models, Peng-Robinson equation of state was
selected as the thermodynamic calculation method, which guaran-
tees accurate calculation results in modeling light gases, alcohols,
and hydrocarbons [7,25]. Before conducting the detailed process
modeling, we carefully compared the simulation results of the
main units such as the reformer (e.g., CH4 conversion, CO2 conver-
sion, and H2/(2CO + 3CO2) ratio in the generated syngas), and the
methanol synthesis reactor (e.g., CO conversion, CO2 conversion,
and methanol yield) with our experimental results to ensure the
accuracy of the proposed models. Besides, the other details about
the process modeling can be found in our previous study [24].
The reforming unit in both proposed options is composed of
two parts, namely, a prereformer and a reformer. The prereformer
is applied to convert all the C2+ hydrocarbons contained in the
fresh feed NG into methane over a Ni catalyst, under reaction tem-
perature 550 °C and pressure 5 bar (gauge). Meanwhile, the equi-
librium type reactor model RGibbs is used to simulate the
prereformer, according to the Gibbs free energy minimization
[7,8]. In addition, the RGibbs equilibrium reactor model is also
applied to simulate the reformer, and three typical reactions for
SRM, CDM, and water-gas shift (WGS) are shown as follows:
SRM : H2 O þ CH4 $ CO þ 3H2 ; DH298 K ¼ 206 kJ=mol ð1Þ
CDM : CO2 þ CH4 $ 2CO þ 2H2 ; DH298 K ¼ 247 kJ=mol ð2Þ
WGS : CO þ H2 O $ CO2 þ H2 ; DH298 K ¼ 41 kJ=mol ð3Þ
The reformer is operated under reaction temperature 900 °C
and pressure 5 bar (gauge). Under this condition, the three reac-
tions mentioned above can be assumed to reach chemical equilib-
rium, given that the reaction rates are very fast at such an elevated
temperature. Meanwhile, ‘‘restricted chemical equilibrium” option
is selected to better simulate the reformer.
After reforming, the generated syngas directly enters into the
methanol synthesis unit without using any syngas ratio condition-
ing unit, since the flexible syngas ratios can be achieved by adjust-
ing the two competitive methane reforming reactions SRM and
CDM, as mentioned above. In the methanol synthesis reactor,
hydrogenation of CO2 and CO occurs over a Cu-based catalyst
 C. Zhang et al. / Fuel xxx (2016) xxx–xxx 3

Recycle to reforming unit

RE-REFO

PRO-RE1 Reformer
E-102 PRE-REFO E-103
MIXER E-101
E-104 REFORMER
MIX-1 MIX-2 PROPR
NG
NG MIX PROPR1 PROPR2 Vent Gas
H2O
Steam
PRO-RE2
Prereformer PRO-RE VENT

RE-MSR

FS-1 FS-2
E-105
Recycle to methanol synthesis unit
GAS RECYCLE
SYNGAS
C-101 E-107

PRODSR1 V-102
V-101
Splitting recycle
PRO-RE3
Option 1 Option 2 CMEOH
SYNGAS1
PRODSR
WW Crude Methanol
PROMSR
B1 E-106

SYNGAS2 MSRFEED
CO2 CO2
MSR
DSR

Methanol Reactor

Fig. 1. Schematic process diagram of the two proposed CGTM process options 1 and 2.

under suitable hydrogen content (i.e., H2/(2CO + 3CO2) = 1–1.1).
The operating temperature and pressure of the methanol synthesis
reactor are 250 °C and 80 bar (gauge), respectively. The main reac-
tions in the methanol synthesis reactor are expressed as follows:
CO2 þ 3H2 $ CH3 OH þ H2 O; DH298 K ¼ 49:5 kJ=mol
CO þ 2H2 $ CH3 OH; DH298 K ¼ 90:5 kJ=mol
CO2 þ H2 $ CO þ H2 O; DH298 K ¼ 41:2 kJ=mol
The RPlug reactor model is selected to simulate the methanol
synthesis reactor, and the Langmuir-Hinshelwood-Hougen-Wat
son (LHHW) kinetic approach is applied in the RPlug model to sim-
ulate the aforementioned three reactions (Eqs. (4)–(6)). The kinetic
parameters applied in the LHHW model are obtained from the pre-
vious experimental results [26]. Other detailed parameters of the
methanol synthesis reactor are shown in our previous work [24].
After methanol synthesis, a gas stream is discharged from the
top outlet of the methanol synthesis reactor, which contains unre-
acted syngas, methane, nitrogen, etc. Meanwhile, a liquid stream is
discharged from the reactor bottom outlet, which contains the tar-
get product methanol, few byproducts such as DME, ethanol, and
water. A portion of the unreacted syngas is vented to suppress
the accumulation of inert gases, and applied as fuel gas to save
the fuel NG. The remaining unreacted syngas is recycled to the
reforming and/or methanol synthesis units to enhance the CO2
conversion as well as energy efficiency of the two proposed CGTM
options.
2.2. Total capital investment and product cost estimation
The estimated capital investment for the main pieces of equip-
ment is listed in Table 1. The capital investments of several pieces
of equipment such as the reformer and methanol synthesis reactor
ð4Þ
were determined via the six-tenth factor rule based on the refer-
ence capital cost data first, and then updated to the year 2015
ð5Þ
using the annual chemical engineering plant cost index (CEPCI)
to account for the price development effect [27]. The capital invest-
ð6Þ
ment of other pieces of equipment such as heat exchangers and
separators was calculated by ourselves as per the works of Peter
and Walas et al. [27,28].
The total capital investment (TCI) was determined by ratio esti-
mation, based on the capital investment of the main pieces of
equipment, as shown in Eq. (7), and the calculation results are
summarized in Table 2 [7,23]. Besides, the ratio factors used in
the present study were selected according to the recommended
ratio factors for fluid processing plant by Peter and Timmerhaus
[27].
!
X
n
TCI ¼ IE  1 þ RF i ð7Þ
i¼1
where RFi is the ratio factor for direct, indirect and working capital, i
is the item (1.2)–(1.8), (2.1)–(2.5) and (3) listed in Table 2, IE is the
investment of the main pieces of delivered equipment.
The total product cost (TPC) was calculated by Eq. (8) based on
the economic assumptions listed in Table 3.

Table 1
Main equipment cost estimation.

No. Description Cost/M$, Cost/M$, Cost/M$, Ref.

OP.1, S/C = 1.5 OP.1, S/C = 2.5 OP.2, S/C = 2.5
2015 2015 2015
1 Pre-reformer 0.71 0.9 0.89 [7]
2 SCR reformer 34.79 40.98 41.08 [7]
3 Furnace 10.41 12.26 12.29 [7]
4 MSR reactor 39.84 46.08 55.74 [29]
5 Water -syngas separator 0.41 0.47 0.56 This work
6 Crude methanol separator 0.67 0.82 1.05 This work
7 Syngas compressor 22.14 25.22 25.54 [29]
8 Waste heat boiler 3.71 4.45 4.46 This work
9 Heaters 7.42 9.23 9.27 This work
10 Coolers 6.76 7.98 7.97 This work
Total purchased equipment cost 126.86 148.39 158.85
Total purchased equipment cost (delivered) 139.55 163.23 174.74

Please cite this article in press as: Zhang C et al. Carbon dioxide utilization in a gas-to-methanol process combined with CO2/Steam-mixed reforming:
Techno-economic analysis. Fuel (2016), http://dx.doi.org/10.1016/j.fuel.2016.11.008
4 C. Zhang et al. / Fuel xxx (2016) xxx–xxx

Table 2
Total capital investment estimation.

Item Ratio factor Cost/M$, Cost/M$, Cost/M$,

OP.1, S/C = 1.5, OP.1, S/C = 2.5, OP.2, S/C = 2.5,
2015 2015 2015
1. Direct cost
1.1 Purchased equipment (delivered) 1.00 139.55 163.23 174.74
1.2 Purchased equipment installation 0.47 65.59 76.72 82.13
1.3 Instrumentation & Controls 0.36 50.24 58.76 62.91
1.4 Piping 0.68 94.89 111.00 118.82
1.5 Electrical systems 0.11 15.35 17.96 19.22
1.6 Buildings (including services) 0.18 25.12 29.38 31.45
1.7 Yard improvements 0.10 13.96 16.32 17.47
1.8 Service facilities 0.70 97.69 114.26 122.32
Total direct costs 502.38 587.63 629.06
2. Indirect cost
2.1 Engineering and supervision 0.33 46.05 53.87 57.66
2.2 Construction expenses 0.41 57.22 66.92 71.64
2.3 Legal expenses 0.04 5.58 6.53 6.99
2.4 Contractor’s fee 0.22 30.70 35.91 38.44
2.5 Contingency 0.44 61.40 71.82 76.89
Total indirect costs 200.95 235.05 251.63
3. Working capital (WC) 0.89 124.20 145.27 155.52
Fixed capital investment (FCI) 703.33 822.68 880.69
Total capital investment (TCI) 827.53 967.95 1036.21

Table 3
Summary of the economic assumptions for total product cost estimation.

Item Economic assumptions

(1) Raw material Natural gas 3 $/MMBTU, process water 0.33 $/Mt
(2) Utilities Cooling water 0.033 $/Mt, electricity 0.063 $/kW h
(3) Operating & maintenance
(3.1) Operating labor 60 labors/shift, 3 shift/day, 60,000 $/labor/year
(3.2) Supervisory & clerical labor 20% of operating labor
(3.3) Maintenance & repairs 6% of fixed capital investment
(3.4) Operating supplies 15% of maintenance and repairs (3.3)
(3.5) Laboratory charges 15% of operating labor
(4) Patents & royalties 1% of total product cost
(5) Depreciation Recovery period 20 years, salvage value 5%, linear
(6) Local taxes & insurance 2% of fixed capital investment
(7) Plant overhead costs 60% of (3.1 + 3.2 + 3.3)
(8) General expenses
(8.1) Administration 20% of (3.1 + 3.2 + 3.3)
(8.2) Distribution & selling 5% of total product cost
(8.3) Research & development 4% total product cost
(9) Total product cost (1) + (2) + (3) + (4) + (5) + (6) + (7) + (8)

Table 4
TPC ¼ C RM þ C U þ C O&M þ C P&R þ C D þ C T&I þ C PO þ C GE ð8Þ Economic analysis assumptions.

where CRM, CU, CO&M, CP&R, CD, CT&I, CPO and CGE are the costs of raw Item Economic assumptions
material, utility, operating and maintenance, patent and royalty, 1. Steam Self-produced
depreciation, local tax and insurance, plant overhead, and general 2. Project life 20 years
expenses, respectively [23]. In the TPC calculation, depreciation cost 3. Plant uptime 350 days/year
4. Construction period & capital 3 years (1st 15%, 2nd 35%, 3rd 50%)
CD represents the capital investment. In addition, a linear deprecia-
distribution
tion method was selected to calculate the annual depreciation cost, 5. Construction inflation rate 2%/year
with an assumption of a 20-year recovery period and 5% salvage 6. Start-up cost 10% of FCI
value. Other costs shown in Eq. (8), such as CPO and CGE were deter- 7. On stream factor of each year (1st 50%, 2nd 90%, 3rd–20th 100%)
8. Income tax rate 35%
mined by ratio estimation [27].
9. Hurdle rate 12%
10. Methanol price [30] 400 $/Mt
2.3. Economic analysis 11. Plant location U.S. Gulf

Before we conduct the economic analysis, several economic

assumptions were adopted, as shown in Table 4. Besides, several X
n
CF t
NPVðt; nÞ ¼ t ð9Þ
key indicators, such as NPV, IRR, and DPBP, were selected to assess ð1 þ iÞ
t¼0
the profitability of the two proposed CGTM options. The specific
method for NPV and DPBP calculation are shown in the following where CF is the cash flow, t is the year of the cash flow, i is the dis-
Eqs. (9) and (10), respectively. count rate, and n is the total number of years.

Please cite this article in press as: Zhang C et al. Carbon dioxide utilization in a gas-to-methanol process combined with CO2/Steam-mixed reforming:
Techno-economic analysis. Fuel (2016), http://dx.doi.org/10.1016/j.fuel.2016.11.008
 C. Zhang et al. / Fuel xxx (2016) xxx–xxx 5

DPBP ¼ Ny þ jC n j=C p ð10Þ 3. Results and discussion

where Ny is the number of years when the last negative value of
3.1. Process simulation results
cumulative discounted cash flow happens after the initial capital
investment, Cn is the last negative cumulative discounted cash flow,
The overall mass and energy stream results as well as the ther-
and Cp is the discounted cash flow of the year when the first positive
mal and carbon efficiency of the two proposed CGTM options 1 and
value of cumulative discounted cash flow occurs. The IRR is defined
2 are listed in Table S2 (see SI). As shown in Table S2, the methanol
as the discount rate i at which the NPV equals to zero, thus, it can be
productivity is same for both options. However, the consumption
determined by adjusting the item i in Eq. (9). In addition, the criteria
of fresh feed NG in option 1 is lower than that of option 2. This
for the economic evaluation in the present work are made as fol-
is due to the higher CO2 conversion via CO2 reforming, compared
lows: the minimum acceptable IRR and the base DPBP values are
to the CO2 hydrogenation via methanol synthesis. On the contrary,
set as 12% and 10 years, respectively [7,23,32].
Capital investment of OP.1 (1000 $/TPD)

300 30
Delivered equipment investment
28
250 Total direct costs
Total indirect costs 26
Working capital
200 Total capital investment 24

IRR (%)
150 22

20
100 Methanol price
18 NG price
CAPEX
50 Fixed direct OPEX
16
Variable OPEX (excl. NG)
0 14
0 5000 10000 15000 20000 -20% -10% 0% 10% 20%
Plant scale of OP.1, S/C=1.5 (TPD) % Variation in prices and costs of OP.1 (S/C=1.5)
(a) (d)
350 26
Capital investment of OP.1 (1000 $/TPD)

Delivered equipment investment

300 Total direct costs
24
Total indirect costs 22
250 Working capital
Total capital investment 20
IRR (%)

200
18
150
16
Methanol price
100 NG price
14
CAPEX
50 12 Fixed direct OPEX
Variable OPEX (excl. NG)
0 10
0 5000 10000 15000 20000 -20% -10% 0% 10% 20%
Plant scale of OP.1, S/C=2.5 (TPD) % Variation in prices and costs of OP.1 (S/C=2.5)
(b) (e)
350 24
Capital investment of OP.2 (1000 $/TPD)

Delivered equipment investment

300 Total direct costs 22
Total indirect costs
20
250 Working capital
Total capital investment
18
IRR (%)

200
16
150
14
Methanol price
100 NG price
12
CAPEX
50 10 Fixed direct OPEX
Variable OPEX (excl. NG)
0 8
0 5000 10000 15000 20000 -20% -10% 0% 10% 20%
Plant scale of OP.2, S/C=2.5 (TPD) % Variation in prices and costs of OP.2 (S/C=2.5)
(c) (f)
Fig. 2. Effects of plant scale on the capital investments (a, b, and c) and sensitivity analysis of both CGTM options 1 and 2 at the plant scale of 5000 TPD (d, e, and f).

Please cite this article in press as: Zhang C et al. Carbon dioxide utilization in a gas-to-methanol process combined with CO2/Steam-mixed reforming:
Techno-economic analysis. Fuel (2016), http://dx.doi.org/10.1016/j.fuel.2016.11.008
6 C. Zhang et al. / Fuel xxx (2016) xxx–xxx

the amount of fuel NG consumed in option 1 is higher than that of Table 5

option 2, which is because of the highly endothermic CRM reaction. Economic evaluation results for both CGTM options 1 and 2.

As for the energy efficiency, the thermal and carbon efficiency of Item OP.1 S/C = 1.5 OP.1 S/C = 2.5 OP.2 S/C = 2.5 Unit
option 2 at a steam-to-carbon (S/C) ratio of 2.5 is around 0.4% Plant scale 5000 5000 5000 TPD
higher than that of option 1 (S/C = 2.5), which is mainly because NPV (ic = 12%) 858.80 598.74 483.41 M$
of the higher fuel NG consumption in the reformer as well as the IRR 22.65 18.70 17.15 /
lower CO2 conversion in the methanol synthesis reactor of option DPBP 6.23 8.29 9.52 yr

1. Whereas, the thermal and carbon efficiency of option 2

(S/C = 2.5) is about 1% lower than that of option 1 (S/C = 1.5), which
is mainly due to the lower S/C ratio. Thus, from the technical point
of view, at the same S/C ratio of 2.5, compared with option 1,
option 2 seems to be more conducive to CO2 utilization in the pro-
posed CGTM process, considering its higher thermal and carbon
efficiency. However, from the economic point of view, the situation
could change because of the capital cost increase in option 2, which
will be further discussed in the following sections.
3.2. Total capital investment and product cost estimation
The estimated capital investments for the base cases of both
CGTM options are shown in Table 2. The total capital investment
of option 2 is 1036.21 M$, which is around 7% and 25% higher than
that of option 1 at S/C ratios of 2.5 and 1.5, respectively. This is
mainly due to the higher equipment costs of option 2, given that
the amount of the fresh feedstock and the produced syngas
of option 1 is lower than that of option 2, especially for option 1
(S/C = 1.5), as can be confirmed from Tables 1 and S2 (see SI).
In general, the plant capacity of a GTM process has a great influ-
ence on its plant economy, which is known as the ‘‘scale economy”.
This is due to the fact that the capital investment on unit product
basis decreases with increasing plant capacity. On the basis of the
six-tenth-factor rule, capital investments of both CGTM options 1
and 2 at different plant capacities are determined and illustrated
in Fig. 2a–c. The figures show that the capital investments gradu-
ally decrease with the increase of plant scale. As the plant scale
increases from 2500 to 20,000 TPD, the TCI of option 1 at S/C ratios
of 1.5 and 2.5 decreases from 268.22 K$/TPD to 109.19 K$/TPD, and
313.28 K$/TPD to 127.53 K$/TPD, respectively. While, the TCI of
option 2 decreases from 335.86 K$/TPD to 136.72 K$/TPD. In addi-
tion, the scale benefit seems to be significant in the capacity range
of 2500–10,000 TPD, considering that the decreasing rate is rela-
tively larger compared to the range of 10,000–20,000 TPD.
Fig. 3 shows the production cost distribution for the base cases
of both proposed CGTM options 1 and 2. As shown in Fig. 3, the
total product cost of option 2 is 222.35 $/Mt, which is 24.04 $/Mt
and 6.57 $/Mt higher that of option 1 at S/C ratios of 1.5 and 2.5,
respectively. This is mainly due to the lower capital investment
as well as the fresh feedstock consumption of option 1, although
option 2 requires less amount of fuel NG. As can be seen from
Fig. 3, the raw material costs as well as the capital investment
related costs such as depreciation and maintenance occupy most
portion of the TPC, which means the TPC seems to be highly
affected by the capital cost and the prices of fresh feedstock. As
mentioned before, the capital investment related costs could be
reduced by expanding the plant capacity. Consequently, the TPC
would be further reduced, which will be discussed in the following
economic analysis section in detail.
3.3. Economic evaluation
The economic evaluation results for the base cases of both
CGTM options 1 and 2 are listed in Table 5. As we can see, the
NPV values of both options are considerably higher than zero,
and option 1 (S/C = 1.5) gives the highest NPV of 858.80 M$, which
is 260.06 M$, and 375.39 M$ higher than those of options 1 and 2
at a S/C ratio of 2.5, respectively. Meanwhile, the IRR values of both
options are also higher than the minimum acceptable IRR of 12%,
and the IRR of option 1 (S/C = 1.5) is determined to be 22.65%,
which is 3.95% and 5.50% higher than those of options 1 and 2 at
the S/C ratio of 2.5, respectively. These results are in good agree-
ment with the previous study [33], in which the IRR value for the
5000 TPD methanol project utilizing the high CO2 containing NG
was estimated to be in the range of 20–25%. In addition, the DPBP
values of both options are lower than the base DPBP of 10 years as
well, and the DPBP value of option 1 (S/C = 1.5) is shown to be
6.23 year, which is 2.06 year and 3.29 year shorter than those of
options 1 and 2 at the S/C ratio of 2.5, respectively. On the basis
of the above evaluation results, the base cases of both CGTM
options fulfill all the evaluation criteria, and considering the higher

250
General expenses

200 Plant overhead costs

Total product cost ($/Mt)

Local taxes and insurance

150
Depreciation

Patents and royalties

100

Operating and maintenance

50
Utilities

Raw material
0
OP.1 (S/C=1.5) OP.1 (S/C=2.5) OP.2 (S/C=2.5)

Fig. 3. Total product cost of both CGTM options 1 and 2 at base cases.

Please cite this article in press as: Zhang C et al. Carbon dioxide utilization in a gas-to-methanol process combined with CO2/Steam-mixed reforming:
Techno-economic analysis. Fuel (2016), http://dx.doi.org/10.1016/j.fuel.2016.11.008
 C. Zhang et al. / Fuel xxx (2016) xxx–xxx 7

NPV and IRR values as well as lower DPBP value, option 1 seems to
be more economically feasible than option 2, especially for option
1 at a lower S/C ratio of 1.5. This is due to option 1’s lower capital
cost, as mentioned before.
3.4. Sensitivity analysis
After the economic evaluation for the base cases of both CGTM
options, we also conducted sensitivity analysis to investigate the
effects of uncertainties of some important factors (e.g., methanol
price, NG price, CAPEX, and OPEX) on the profitability of both
CGTM options, and the analysis results are shown in Fig. 2d–f. As
we can see, the methanol price, CAPEX, and NG price are the most
sensitive factors, while the fixed direct OPEX, and variable OPEX
are less so. Thus, the methanol price, NG price, and CAPEX will
be the main focus of the following analysis. Besides, the plant scale
was instead selected as the independent variable to show the
effects of CAPEX.
3.4.1. Effects of methanol price on IRR
Fig. 4a shows the effects of the methanol prices on the IRR of the
two proposed CGTM options. As we can see, the IRR values of both
CGTM options gradually decrease as the methanol price decreases.
Meanwhile, in the methanol price range of 300–500 $/Mt, the IRR
values of option 1 (S/C = 1.5) and option 1 (S/C = 2.5) are 3.55–
4.54%, and 1.31–1.77% higher than that of option 2 (S/C = 2.5),
respectively. This can be mainly attributed to the lower capital
investment of option 1, especially at a lower S/C ratio. Moreover,
the IRR values of options 1 and 2 at the S/C ratio of 2.5 decrease
to 12% as the methanol price goes down to around 300 $/Mt, which
indicates that both options 1 and 2 at the S/C ratio of 2.5 would be
economically infeasible as the methanol price falls below 300 $/Mt
at the plant scale of 5000 TPD.
3.4.2. Effects of plant scale on IRR
As mentioned before, the GTM plant scale has vital impacts on
its process economy. Fig. 4b shows the effects of plant scale on the
IRR of both CGTM options. As we can see, the IRR values of both
options increase as the plant scale increases. However, the increas-
ing rate becomes slower in the relatively high plant scale range of
10,000–20,000 TPD. This phenomena is similar to the impacts of
plant scale on the capital investment, as shown above. As the plant
scale increases from 2500 to 20,000 TPD, the IRR value of option 1
(S/C = 1.5) increases from 9.70% to 31.20%, and the IRR values of
options 1 and 2 at the S/C ratio of 2.5 increase from 6.40% to
26.55%, and 5.12 to 24.77%, respectively. Furthermore, the two pro-
posed CGTM options 1 and 2 would be economically infeasible if
the plant scale is lowered down to about 1000 TPD.
3.4.3. Effects of NG price on IRR
The effects of NG prices on the IRR of the two proposed CGTM
options are shown in Fig. 4c. As we can see, the IRR values of both

35 30
OP.1, S/C=1.5
OP.1, S/C=1.5
30 OP.1, S/C=2.5
25 OP.1, S/C=2.5
OP.2, S/C=2.5
OP.2, S/C=2.5
25
20
IRR (%)

IRR (%)

20

15
15 IRR=12%
IRR=12%
10
10

5 5
300 350 400 450 500 1 2 3 4 5 6
Methanol price ($/Mt) NG price ($/MMBTU)
(a) (c)
35
OP.1, S/C=1.5
OP.1, S/C=2.5 24
30
OP.2, S/C=2.5
25 OP.1, S/C=1.5
22
OP.1, S/C=2.5
IRR (%)

20 OP.2, S/C=2.5
IRR (%)

20
15
IRR=12%
10 18

5
16
0
0 25 50 75 100 125 150 175 200 0 20 40 60 80
Plant scale (100 TPD) Carbon tax ($/Mt CO2)
(b) (d)
Fig. 4. Effects of several factors on the IRR of both CGTM options: (a) methanol price; (b) plant scale; (c) NG price; (d) carbon tax.

Please cite this article in press as: Zhang C et al. Carbon dioxide utilization in a gas-to-methanol process combined with CO2/Steam-mixed reforming:
Techno-economic analysis. Fuel (2016), http://dx.doi.org/10.1016/j.fuel.2016.11.008
8 C. Zhang et al. / Fuel xxx (2016) xxx–xxx
options decrease with the increase of NG prices. With the NG price
increasing from 1 to 6 $/MMBTU, the IRR value of option 1
(S/C = 1.5) decreases from 27.57% to 14.01%, and the IRR values
of options 1 and 2 at the S/C ratio of 2.5 decrease from 23.33% to
10.29%, and 21.63% to 9.02%, respectively. Meanwhile, the IRR dif-
ferences between options 1 and 2 decrease as the NG prices
increase, which is mainly because of the decreasing costs of fuel
NG in option 2. In addition, options 1 and 2 at the S/C ratio of 2.5
would be economically infeasible when the NG price rises up to
around 6 $/MMBTU at the plant scale of 5000 TPD.
3.4.4. Effects of carbon tax on IRR
In this work, the effects of carbon tax were investigated by
using the reduced CO2 emissions of the two proposed CGTM
options, compared to the conventional GTM process [24]. Mean-
while, the carbon tax was set in the following range of 0–80
$/Mt CO2 [7,31]. Fig. 4d shows the effects of carbon tax on the
IRR of both CGTM options. As we can see from Fig. 4d, the IRR val-
ues of both options 1 and 2 monotonously increase as the carbon
tax increases. More specifically, with the carbon tax rising from 0
to 80 $/Mt CO2, the IRR values of option 1 (S/C = 1.5) increase from
22.65% to 24.30%, and the IRR values of options 1 and 2 at the
S/C ratio of 2.5 increase from 18.70% to 20.19%, and 17.15 to
18.59%, respectively. This means the two proposed CGTM options
would be more favorable on consideration of the growing stringent
environmental protection policies.
3.5. Break-even analysis
The break-even analysis assumes that different views can be
adopted in terms of NG and methanol prices, indicating the price
combinations, at which the NPV value equals to zero, i.e., the price
combinations which can earn a minimum acceptable IRR of 12%.
Fig. 5 shows the break-even analysis results for the two proposed
CGTM options at the base case CAPEX and the worst case CAPEX
(assuming a 40% increase). As expected, as NG prices rise up,
methanol prices should also increase to compensate an increase
in NG costs, by generating more revenues. Besides, any price com-
binations located above the break-even lines are NPV positive
alternatives. At the NG price of 3 $/MMBTU, option 1 (S/C = 1.5)
breaks even with the methanol price of 293.25 $/Mt, and options
1 and 2 at the S/C ratio of 2.5 break even with the methanol prices
of 326.43 $/Mt and 340.90 $/Mt, respectively. Furthermore, if the
worst case CAPEX occurs, assuming a 40% increase, according to
600
OP.1, S/C=1.5, Base CAPEX
550 OP.1, S/C=2.5, Base CAPEX
OP.2, S/C=2.5, Base CAPEX
OP.1, S/C=1.5, +40% CAPEX
500
Methanol price ($/Mt)
OP.1, S/C=2.5, +40% CAPEX
OP.1, S/C=1.5, +40% CAPEX
450
400
350
300
250
200
1 2 3 4
NG price ($/MMBTU)
Fig. 5. Break-even analysis for both CGTM options 1 and 2 at the base and worst
CAPEX cases.
Please cite this article in press as: Zhang C et al. Carbon dioxide utilization in a gas-to-methanol process combined with CO2/Steam-mixed reforming:
Techno-economic analysis. Fuel (2016), http://dx.doi.org/10.1016/j.fuel.2016.11.008
the present cost estimation method’s typical accuracy range,
option 1 (S/C = 1.5) breaks even with the methanol price of
363.51 $/Mt, and options 1 and 2 at the S/C ratio of 2.5 break even
with the methanol prices of 408.50 $/Mt and 428.83 $/Mt,
respectively.
4. Conclusion
Aiming at efficient utilization of CO2 in the GTM process, we
suggested two CGTM options 1 and 2 with the fresh CO2 feeding
method as the main configuration difference. In option 1, the fresh
CO2 was first fed to the reforming unit to produce CO, and then to
the methanol synthesis unit to produce methanol. While, in option
2, the fresh CO2 was fed to the methanol synthesis unit to directly
produce methanol. Both CGTM options can effectively utilize CO2
and enhance the thermal and carbon efficiency of the GTM process,
via CO2/Steam-mixed reforming and CO2 hydrogenation. Economic
evaluation for the base cases of both proposed CGTM options were
conducted to evaluate their economic feasibility via the selected
economic evaluation indicators NPV, IRR, and DPBP. The NPV,
IRR, and DPBP values for the base cases of the proposed CGTM
options were determined to be in the rage of 483.41–858.80 M$,
17.15–22.65%, and 6.23–9.52 year, respectively. Besides, sensitivity
analysis as well as break-even analysis were further implemented
to investigate the profitability of the two proposed CGTM options
under various circumstances. The sensitivity analysis results indi-
cated that methanol price, CAPEX, and NG price were the most sen-
sitive factors. Therefore, the effects of methanol price, plant scale,
NG price, together with carbon tax on the economic performance
of both CGTM options were investigated further in detail. It was
shown that both CGTM options were economically feasible
provided that the methanol price, NG price, and the plant scale
range were located in the following range of 350–500 $/Mt, 1–5
$/MMBTU, and 2500–5000 TPD, respectively, according to the
economic evaluation indicators NPV, IRR, and DPBP, and were more
economically competitive in the case of higher plant scale and
carbon tax.
Acknowledgment
This work was supported by Korea Institute of Energy Technol-
ogy Evaluation and Planning (KETEP) under ‘‘Energy Efficiency &
Resources Programs” (Project No. 2012T100201578) of the
Ministry of Trade, Industry & Energy, Republic of Korea.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2016.11.008.
References
[1] Appel AM, Bercaw JE, Bocarsly AB, Dobbek H, DuBois DL, Dupuis M, et al.
Frontiers, opportunities, and challenges in biochemical and chemical catalysis
of CO2 fixation. Chem Rev 2013;113:6621–58.
[2] Rezayee NM, Huff CA, Sanford MS. Tandem amine and ruthenium-catalyzed
hydrogenation of CO2 to methanol. J Am Chem Soc 2015;137:1028–31.
[3] Zhang CD, Jun K-W, Ha K-S, Lee Y-J, Kang SC. Efficient utilization of greenhouse
gases in a Gas-to-Liquids process combined with CO2/Steam-mixed reforming
and Fe-based Fischer-Tropsch synthesis. Environ Sci Technol 2014;48:8251–7.
[4] Min J-E, Lee Y-J, Park H-G, Zhang C, Jun K-W. Carbon dioxide reforming of
methane on Ni–MgO–Al2O3 catalysts prepared by sol–gel method: effects of
Mg/Al ratios. J Ind Eng Chem 2015;26:375–83.
5 6
[5] Olah GA, Goeppert A, Czaun M, Prakash GS. Bi-reforming of methane from any
source with steam and carbon dioxide exclusively to metgas (CO–2H2) for
methanol and hydrocarbon synthesis. J Am Chem Soc 2012;135:648–50.
[6] Wang W, Wang S, Ma X, Gong J. Recent advances in catalytic hydrogenation of
carbon dioxide. Chem Soc Rev 2011;40:3703–27.
 C. Zhang et al. / Fuel xxx (2016) xxx–xxx
[7] Zhang CD, Jun K-W, Gao RX, Lee Y-J, Kang SC. Efficient utilization of carbon
dioxide in gas-to-liquids process: process simulation and techno-economic
analysis. Fuel 2015;157:285–91.
[8] Ha K-S, Bae JW, Woo K-J, Jun K-W. Efficient utilization of greenhouse gas in a
gas-to-liquids process combined with carbon dioxide reforming of methane.
Environ Sci Technol 2010;44:1412–7.
[9] Kang SC, Jun K-W, Lee Y-J. Effects of the CO/CO2 ratio in synthesis gas on the
catalytic behavior in Fischer-Tropsch synthesis using K/Fe–Cu–Al catalysts.
Energy Fuel 2013;27:6377–87.
[10] Yao Y, Liu X, Hildebrandt D, Glasser D. Fischer-Tropsch synthesis using H2/CO/
CO2 syngas mixtures over an iron catalyst. Ind Eng Chem Res
2011;50:11002–12.
[11] Li Z, Li J, Dai M, Liu Y, Han D, Wu J. The effect of preparation method of the Cu–
La2O3–ZrO2/c-Al2O3 hybrid catalysts on one-step synthesis of dimethyl ether
from syngas. Fuel 2014;121:173–7.
[12] Yang R, Yu X, Zhang Y, Li W, Tsubaki N. A new method of low-temperature
methanol synthesis on Cu/ZnO/Al2O3 catalysts from CO/CO2/H2. Fuel
2008;87:443–50.
[13] Bertau M, Offermanns H, Plass L, Schmidt F, Wernicke HJ, editors. Methanol:
the basic chemical and energy feedstock of the future. Berlin
Heidelberg: Springer-Verlag; 2014.
[14] Olah GA. Beyond oil and gas: the methanol economy. Angew Chem Int Ed
2005;44:2636–9.
[15] Yuan Z, Eden MR, Gani R. Toward the development and deployment of large-
scale carbon dioxide capture and conversion processes. Ind Eng Chem Res
2016;55:3383–419.
[16] Julián-Durán LM, Ortiz-Espinoza AP, El-Halwagi MM, Jiménez-Gutiérrez A.
Techno-economic assessment and environmental impact of shale gas
alternatives to methanol. ACS Sustainable Chem Eng 2014;2:2338–44.
[17] Ehlinger VM, Gabriel KJ, Noureldin MM, El-Halwagi MM. Process design and
integration of shale gas to methanol. ACS Sustainable Chem Eng 2013;2:30–7.
[18] Wang Y, Peng J, Zhou C, Lim Z-Y, Wu C, Ye S, et al. Effect of Pr addition on the
properties of Ni/Al2O3 catalysts with an application in the autothermal
reforming of methane. Int J Hydrogen Energy 2014;39:778–87.
[19] Oliveira EL, Grande CA, Rodrigues AE. Methane steam reforming in large pore
catalyst. Chem Eng Sci 2010;65:1539–50.
Please cite this article in press as: Zhang C et al. Carbon dioxide utilization in a gas-to-methanol process combined with CO2/Steam-mixed reforming:
Techno-economic analysis. Fuel (2016), http://dx.doi.org/10.1016/j.fuel.2016.11.008
9
[20] Velasco JA, Fernandez C, Lopez L, Cabrera S, Boutonnet M, Järås S. Catalytic
partial oxidation of methane over nickel and ruthenium based catalysts under
low O2/CH4 ratios and with addition of steam. Fuel 2015;153:192–201.
[21] Kathiraser Y, Thitsartarn W, Sutthiumporn K, Kawi S. Inverse NiAl2O4 on
LaAlO3–Al2O3: unique catalytic structure for stable CO2 reforming of methane.
J Phys Chem C 2013;117:8120–30.
[22] Cheng WH, Kung HH, editors. Methanol production and use. New York: Marcel
Dekker; 1994.
[23] Zhang CD, Jun K-W, Gao RX, Kwak G, Kang SC. Efficient utilization of associated
natural gas in a modular gas-to-liquids process: technical and economic
analysis. Fuel 2016;176:32–9.
[24] Zhang CD, Jun K-W, Kwak G, Lee Y-J, Park H-G. Efficient utilization of carbon
dioxide in a gas-to-methanol process composed of CO2/steam–mixed
reforming and methanol synthesis. J CO2 Util 2016;16:1–7.
[25] Lee C-J, Lim Y, Kim HS, Han C. Optimal gas-to-liquid product selection from
natural gas under uncertain price scenarios. Ind Eng Chem Res
2009;48:794–800.
[26] Lim H-W, Park M-J, Kang S-H, Chae H-J, Bae JW, Jun K-W. Modeling of the
kinetics for methanol synthesis using Cu/ZnO/Al2O3/ZrO2 catalyst: influence of
carbon dioxide during hydrogenation. Ind Eng Chem Res 2009;48:10448–55.
[27] Peter MS, Timmerhaus KD. Plant design and economics for chemical engineers.
4th ed. New York: McGraw Hill; 1991.
[28] Walas SM. Chemical process equipment: selection and design. 2nd
ed. Amsterdam: Elsevier; 1990.
[29] Amirkhas E, Bedi R, Harley S, Lango T. Methanol production in trinidad &
tobago; final report: phase II. University of California: Davis; 2006.
[30] Methanex methanol price. https://www.methanex.com/our-business/pricing
[accessed January 2016].
[31] Center for climate and energy solutions. options and considerations for a
federal carbon tax. http://www.c2es.org/publications/options-considerations-
federal-carbon-tax [accessed January 2016].
[32] You L, editor. Construction project economic evaluation methods and
parameters. Beijing: China Planning Press; 2006 [in Chinese].
[33] http://www.meoaustralia.com.au/icms_docs/77167_06082010_-_NTP68_
Commercialisation_Options_MB.pdf [accessed September 2016].