Article

A General Framework for the Evaluation of

Direct Nonoxidative Methane Conversion
Strategies
Kefeng Huang, James B. Miller,
George W. Huber, James A.
Dumesic, Christos T. Maravelias
maravelias@wisc.edu

HIGHLIGHTS
A framework for the analysis of
natural gas conversion strategies
is proposed

A general systems-level model is

developed and economic
feasibility is assessed

Coke formation appears to be the

major technical bottleneck

Methane one-pass conversion and

ethylene selectivity are the major
economic drivers

Natural gas is a versatile chemical feedstock. While the direct conversion of

methane to olefins and higher hydrocarbons has received significant attention,
there exist a number of open questions regarding the development of cost-
effective methane-to-chemicals integrated processes. To address some of these
questions, we develop a general systems-level framework for the systematic
evaluation of various strategies and the identification of key technology gaps and
economic drivers.

Huang et al., Joule 2, 349–365

February 21, 2018 ª 2018 Elsevier Inc.
https://doi.org/10.1016/j.joule.2018.01.001
Article
A General Framework
for the Evaluation of Direct Nonoxidative
Methane Conversion Strategies
Kefeng Huang,1 James B. Miller,1 George W. Huber,1 James A. Dumesic,1
and Christos T. Maravelias1,2,*

SUMMARY Context & Scale

In this paper, we study single-step natural gas conversion technologies that Natural gas is a versatile and
directly convert methane to olefins and higher hydrocarbons. Despite the rela- relatively clean chemical
tive simplicity of these technologies, the development of processes based on feedstock. The development of
these approaches remains challenging. Accordingly, we utilize process synthe- natural gas conversion
sis and modeling to assess the economic feasibility of direct nonoxidative technologies has recently
methane conversion strategies. We develop a flexible approach that allows received significant attention due
for the systematic evaluation of various technology alternatives and for the to the increase of natural gas
identification of the key technology gaps that must be overcome. The results supply in the United States and
of our analyses demonstrate that an economically feasible direct methane con- low natural gas prices relative to
version process is contingent upon fundamental research advances in the area crude oil. The conversion of
of catalytic conversion to increase methane conversion to hydrocarbon prod- natural gas into chemicals
ucts (e.g., coke formation less than 20% and a minimum conversion to products presents a promising means of
of 25%). Upon this development, further efforts can be devoted to improve utilizing an abundant resource
ethylene selectivity as well as reduce catalyst cost and overall capital costs. while achieving energy security
and mitigating pollutant
emissions. Yet the direct
INTRODUCTION
conversion of methane to olefins
Natural gas, which is primarily composed of methane (80%–95% by volume) and
is still at the basic research level,
other light alkanes, is used mainly as a direct fuel for household and industrial heat-
and it is unclear which of, and to
ing and power generation. In 2016, proven global reserves of natural gas were esti-
what extent, these technologies
mated to be 6,879 trillion cubic feet.1 According to the International Energy Outlook
must be improved to develop a
2016, worldwide annual natural gas consumption is projected to increase from 120
commercial process. Toward this
trillion cubic feet in 2012 to 203 trillion cubic feet in 2040. However, natural gas is
goal, we develop a simple yet
underutilized as a feedstock for the production of liquid transportation fuels and
flexible framework that allows for
chemicals, including synthetic materials and plastics. These ‘‘chemical uses’’ account
the systematic evaluation of
for only 5% of the total natural gas consumption, 70% of which is used for ammonia
various process alternatives and
manufacturing, 20% for methanol synthesis, and the remainder for a variety of chem-
the identification of the key
icals such as hydrogen cyanide, acetylene, oxo chemicals, and others.2
technology gaps.

Before distribution through pipelines, natural gas is first dehydrated, then stripped
of carbon dioxide, hydrogen sulfide, and higher alkanes to produce a fairly pure
methane stream (
93 vol%).3 Besides the primary methane component (for
hydrogen, ammonia, and methanol production), the ethane component can be
converted to ethylene by steam cracking. Likewise, propane and butane compo-
nents can be converted to propylene and butadiene. These olefins are building
blocks for a wide variety of industrial and consumer chemicals, including resins, plas-
tics, and adhesives. Globally, ethylene production was about 150 million tons in
2015, and the worldwide olefin demand is predicted to grow steadily at a rate of

Joule 2, 349–365, February 21, 2018 ª 2018 Elsevier Inc. 349

Figure 1. Methane Conversion Scheme

1.5%–4.1% per year.4 While olefins can also be derived from cracking light petro-
leum naphtha, natural gas condensate is the least expensive feedstock in the United
States. Natural gas liquid feeds (ethane, propane, and n-butane) accounted for
nearly 90% of the fresh feed for United States ethylene plants in 2015 because pro-
duction costs based on pure ethane feeds were half of that based on naphtha due to
the increased shale gas production since 2009.5

Methane can be converted to higher hydrocarbons (e.g., ethylene and aromatics) by

indirect or direct routes, as shown in Figure 1. In indirect routes, natural gas is first
reformed to synthesis gas (syngas), a mixture of CO and H2, which is subsequently
converted to methanol and olefins via a multistep catalytic reaction in a strategy
known as methanol-to-olefins (MTO). Both reforming and MTO steps produce
H2O byproduct, which requires additional separation efforts. The MTO process
has been commercialized by DICP6 and UOP,7 with several other companies having
developed (but not commercialized the technology), including ExxonMobil8 and
Total.7 Catalysts such as SAPO-34,6,9–13 ZSM-5,14,15 and ZSM-2216,17 are used for
MTO. This indirect route is used industrially today, with more than 60% of the capital
cost for methane reforming to syngas.18

The direct routes form C-C bond in a single catalytic step. Methane is pyrolyzed at
high temperature to form acetylene, which can subsequently be hydrogenated to
ethylene.18–21 Pyrolysis-based processes deliver ethylene, acetylene, benzene,
and hydrogen as the main products; high yields of acetylene (
90%) are obtainable
at extreme temperature conditions (>1,700 C) and short reaction time.19 However, it
is difficult to directly produce ethylene at high yield due to high rates of side reac-
tions (e.g., to acetylene, benzene, and coke + tars). Direct oxidative coupling
methane (OCM) strategies, whereby a C-H bond in methane is activated over mixed
metal oxide in the presence of substoichiometric O2 to form ethylene and ethane,
have been widely studied.22–27 Since the OCM process is accompanied by the total
oxidation of methane to water and oxides of carbon, it has not yet been imple-
mented on an industrial scale except for a recent demonstration plant by Siluria
and its partners.28 Direct nonoxidative coupling over Mo/zeolite catalysts to form
aromatics (dehydroaromatization, or DHA) in the absence of O2 has also received 1Department of Chemical and Biological
significant attention.29–33 High coke yields and the catalyst deactivation caused by Engineering, University of Wisconsin–Madison,
coking have also presented a significant barrier to industrial adoption of DHA. Madison, WI 53706, USA
2Lead
Recent attempts to overcome thermodynamic limitations on aromatic yields by se- Contact
lective removal of the hydrogen coproduct include the development of membrane *Correspondence: maravelias@wisc.edu
reactors.34–37 https://doi.org/10.1016/j.joule.2018.01.001

350 Joule 2, 349–365, February 21, 2018

Figure 2. Process Flowsheet of Nonoxidative Strategy
Detailed base case stream information and column conditions are given in Table S1.

Several studies have addressed the synthesis and technoeconomic evaluation of

processes to convert natural gas to C2 and higher hydrocarbons based on the
MTO/OCM/DHA strategy.4,38–45 By comparison, there have been limited studies
on direct and nonoxidative conversion of methane to ethylene.46–50 Notable recent
work includes an ‘‘isolated site’’ FeªSiO2 catalyst49 and PtSn bimetallic catalysts.50
The former catalyst enables a gas-phase chain reaction that yields ethylene, ben-
zene, naphthalene, and hydrogen, without coke deposition and catalyst deactiva-
tion, while the latter catalysts exhibit high activity, selectivity, and stability for
ethylene production.

To evaluate a methane-to-chemicals approach we have first to develop an inte-

grated strategy, which is a significant undertaking because any strategy employing
a nonoxidative catalytic system must include compression and separation sections
for product recovery and purification as well as recovery and recycle of unreacted
methane, along with refrigeration, power generation, and utility sections. Accord-
ingly, the goal of this paper is (1) the synthesis of a process that employs nonoxida-
tive methane coupling and (2) the identification of the major cost and technological
drivers toward the application of this strategy.

PROCESS SYNTHESIS AND MODELING

Process Description
The proposed process is shown in Figure 2 and consists of the following sections: (1)
catalytic conversion (R-1 and E-1); (2) compression (C-1 to C-6, F-1 to F-3, and D-1);
(3) separation and recovery (E-1 to E-4, F-4 to F-7, and D-2 to D-3); (4) refrigeration;
(5) power generation; (6) storage; and (7) utilities.

Catalytic Conversion
We consider the direct and nonoxidative conversion of methane to ethylene and ar-
omatics in a gas-phase catalytic reactor at atmospheric pressure, with four key vari-
ables: conversion temperature (T), methane one-pass conversion (x), selectivity to
major hydrocarbon products (sp), and ethylene selectivity in major hydrocarbon
products (se). Here major hydrocarbon products include ethylene and aromatics,
and the selectivity is calculated on a C-atom basis (i.e., moles of C as major

Joule 2, 349–365, February 21, 2018 351

Table 1. Natural Gas Feedstock Composition
Component Mole Fraction Parameter
CH4 0.940 yCH4
C2H6 0.032 y C2 H 6
C3H8 0.007 y C3 H 8
nC4H10 0.004 yC4 H10
N2 0.016 yN 2
52
The composition is derived from the NETL report after CO2 removal.

hydrocarbon products per mole of methane converted). If we use benzene as

a representative aromatic, then the primary reaction stoichiometry is generally
described as follows (see Supplemental Information for detailed derivation):

sp se sp ð1  se Þ
4  sp ðse + 1Þ
CH4 / C2 H4 + C6 H 6 + 1  sp C + H2 :
2 6 2
We assume that naphthalene is formed from benzene,50,51 and reaches equilibrium
according to

C6 H6 /0:6C10 H8 + 0:6H2 ; DHR2 ðkJ=mol C6 H6 Þ:

Thus, the heat of this endothermic reaction DHR1 (kJ/mol CH4) can be written as fol-
lows, using the proposed conversion condition:

sp se f sp ð1  se Þ
4  sp ðse + 1Þ f
DHR1 = DHC2 H4 + DHR2 + 1  sp DHfC + DHH2  DHfCH4 ;
2 6 2
where DHf is the enthalpy of formation of the corresponding component.

The natural gas feedstock (Stream 1) is assumed to be delivered via pipeline (typi-
cally at 25 C and 31 bar44), with the composition shown in Table 1. The nonhydro-
carbon species (e.g., N2) are assumed to be inert. The natural gas is mixed with
the methane-rich recycle stream (Stream 14), and delivered to the gas-phase reactor
(R-1), which is operated at a pressure of 2 bar. The C2-C4 alkane components are
assumed to reach equilibrium according to

C2 H6 /C2 H4 + H2 ; DHR3 ðkJ=mol C2 H6 Þ

C3 H8 /C3 H6 + H2 ; DHR4 ðkJ=mol C3 H8 Þ
C4 H10 /C4 H8 + H2 ; DHR5 ðkJ=mol C4 H10 Þ:
Thus, the required heat for the entire conversion, DHC (kJ/mol natural gas feed), un-
der the proposed temperature and pressure can be calculated as follows:

DHC = xyCH4 DHR1 + yC2 H6 DHR2 + yC3 H8 DHR3 + yC4 H10 DHR4 :
The value of DHC is a function of T, x, sp, and se. We can obtain the total energy
requirement for R-1 by simply multiplying DHC with the natural gas feed rate.
This approach forms an appropriate scaling variable for sizing R-1 because it re-
flects the effect of temperature, conversion, selectivity, and feed rate on the
reactor.

We assume that the energy required for the reactions is supplied by burning fuel
gas (e.g., fresh natural gas) and the reactor design is similar to the commercial
ethylene pyrolysis furnace. The natural gas feed stream, as well as the treated wa-
ter feed for the power generation section, are first heated in the convection zone
by the effluent of burning flue gas at the radiant zone. Then the natural gas feed
stream enters the reaction zone where it is heated to the conversion temperature
and produces ethylene and coproducts. The reaction product is then cooled by

352 Joule 2, 349–365, February 21, 2018

treated water in a heat exchanger (E-1) and fed to the compression section
(Stream 2), while the treated water is superheated to high-pressure steam for po-
wer generation.

Compression
The raw olefins gas (Stream 2) produced in the catalytic conversion section is sent to
the multistage compression section to increase its pressure and to remove naphtha-
lene and benzene.53,54 The naphthalene (Stream 3, 94.3 wt%) and benzene (Stream
4, 99.0 wt%) products are directly stored, while the remaining light gases (Stream 5,
primarily H2, CH4, and olefins) are ready for cryogenic separation and recovery. The
major difference between the subject process and conventional naphtha pyrolysis
gas compression is the absence of the caustic wash tower for acid gas removal
(CO2 and H2S) and the molecular sieve dryer for water removal.55,56 In the subject
process, the natural gas feedstock is pretreated with removal of CO2 and no acid
gas and water are produced. The detailed design for this section is presented in
Supplemental Information.

Separation and Recovery

The raw olefins with light gases (Stream 5) is the fresh feed to this section, whose
main purpose is to purify the raw mixture of light gases and olefins to be sold as
products and to recover the unconverted methane. The raw olefins and light gases
mixture first goes through cold box (E-1 to E-3) and flash drums (F-4 to F-6) to obtain
a vapor fraction (Stream 6, primarily H2 and methane) and a liquid fraction (Stream 9,
primarily ethylene). The vapor fraction (Stream 6) is then cooled to 167 C in the end
gas heat exchanger (E-4) and fed to hydrogen and methane separator (F-7), produc-
ing hydrogen (95 vol%) in the vapor (Stream 7) and methane (94.5 wt%) in the liquid
(Stream 8). The methane-rich stream is then further expanded to reach a tempera-
ture of 169 C to provide sufficient cooling in E-4. After cryogenic energy recovery,
the hydrogen product is sent to storage while the methane-rich stream is recycled
back to R-1 throttle.

The liquid raw olefins from F-4 to F-6 (Stream 9) are sent to the demethanizer column
(D-2) to separate methane from C2+ hydrocarbons. Methane (Stream 10) is recov-
ered at the top and recycled back to R-1 after recovering cryogenic energy in cold
box, while the bottom (Stream 11) is further sent to the ethylene fractionator (D-3).
The distillation column, which operates at 19 bar, recovers more than 99% of the
ethylene at the top with a purity of 99.95 vol% (Stream 12). The bottom stream
(Stream 13, mainly containing benzene, C3H6, and nC4H10) can be sent to a further
distillation column to obtain high-value propylene if needed. However, this distilla-
tion is not considered in this work since the bottom stream has a relatively small flow
rate. The liquid ethylene product is finally sent to the storage section and stored
at 30 C and 19 bar.

Refrigeration
Refrigeration plays a critical role in the process due to the large refrigeration duty
for cryogenic separations and the high cost of refrigeration. Thus, a mixed refrig-
erant is designed. It uses a mixture of hydrogen, methane, ethylene, and propylene
(see Table S2 for the base case compositions) to improve the refrigeration thermo-
dynamic efficiency and reduce capital investment, while lowering plant mainte-
nance costs.57–63 The refrigeration section hereby supplies cryogenic cooling
(down to 149 C) for the cold box and condensers of the demethanizer and
ethylene fractionator. The design and specification for this section are discussed
in more detail in Supplemental Information.

Joule 2, 349–365, February 21, 2018 353

Table 2. Key Process Variables Used in Model
Variable Unit Base Case Range

Conversion temperature T C 800 700–1,200
Methane one-pass conversion x % 25 10–100
Selectivity in major hydrocarbon products sp % 100 80–100
Ethylene selectivity in major hydrocarbon se % 20 10–100
products

Storage
This section provides bulk storage for final products, including ethylene, benzene,
and naphthalene. The hydrogen product is distributed directly to downstream users
through a pipeline.

Power Generation
The purpose of this section is to recover the heat from the high-temperature conver-
sion section for steam and power generation. After meeting all process heating and
power demands, surplus electricity is sold to the grid. The design basis of this sec-
tion is given in Supplemental Information, while the overall design and cost basis
assumptions for this section are maintained as the National Engergy Technology
Laboratory (NETL) report.52

Utilities
This section provides the utilities required by the entire process (cooling water, pro-
cess water, and electricity), except steam and refrigerant, which are provided by the
power generation and refrigeration sections, respectively. In addition, a reverse
osmosis unit is used for wastewater treatment to allow the reuse of the process
wastewater from the boiler blowdown and cooling tower blowdown. The details
for the design of this section are given in Supplemental Information, and the cost
estimation follows the basis of the National Renewable Energy Laboratory report.64

Process Modeling
Design Basis and Assumptions
The model of the process was developed in Aspen Plus based, initially, on the exper-
imental data (see Table 2) from Guo et al.49 and Gerceker et al.50 While coke forma-
tion is a critical issue for most current indirect methane conversion routes, accessing
the impact of this factor quantitatively is challenging, especially when coke forma-
tion is substantial because it hampers the continuous operation of the process.
Furthermore, since one of the goals of this paper is to provide targets for commercial
development of direct conversion technologies, we study combinations of process
parameters that, although unattainable today, when materialized may lead to (1)
processes that can be operated continuously and (2) economic metrics that would
make such technologies competitive. Specifically, we consider sp = 80%–100%,
that is, a maximum of 20% of the methane forms coke. Decoking is typically accom-
plished by combustion of the coke particles.2 This operation is followed by oxidation
of the active metal promoters, adjustment of the chloride balance, drying of the
catalyst to remove unwanted moisture, and finally reducing the metal promoters.
This typical catalyst regeneration process occurs in a stepwise, semi-regenerative
fashion.65

Equipment costs were estimated using an exponential scaling expression based on

equipment size and cost data from Aspen Process Economic Analyzer and the liter-
ature (see Table S3 for details). Utility and water requirements for each section are

354 Joule 2, 349–365, February 21, 2018

estimated using linear scaling methods (see Table S4) and used, in conjunction with
prices and cost parameters (Table S5), to estimate operating costs. All costs are in-
dexed to year 2015 using the Chemical Engineering Plant Cost Index. In the base
case design, the natural gas feedstock flow rate is 10 MMSCF/hr. The facility on-
stream time is 7,884 hr per year.

A pioneer plant analysis is carried out to estimate the capital cost growth and plant
performance associated with the construction and operation of such a first-of-kind
plant.66 The methodology, which appropriately accounts for the risk associated
with developing a pioneer process, is developed based on statistical regressions
of industrial data for plant performance and cost growth (see details in Table S6).

Process Simulation
The base case process is modeled using the Aspen Plus PR-BM property
method,67,68 which is recommended for hydrocarbon processing applications. To
assess the impact of potential technology improvements (e.g., one-pass methane
conversion), market conditions (e.g., natural gas price), and design specifications
(e.g., plant scale), we perform approximately 105 simulations. To carry them out
effectively, we develop surrogate unit models and a database that allows us to calcu-
late key flows. For example, we express component flows of Stream 2 as a function of
natural gas feed rate as well as key process variables including T, x, sp, and se. In a
similar manner, we obtain the corresponding fuel gas requirement and recovered
heat for power generation, and thus the capital and operating costs, using scaling
methods for any combination of T, x, sp, se, and natural gas feed rate. The details
are presented in Supplemental Information.

Economic Evaluation
Once equipment costs are determined, direct and indirect cost factors (e.g., instal-
lation costs and project contingency) are applied to estimate the total capital invest-
ment (TCI). The TCI, along with the operating costs, is used in a discounted cash flow
analysis (see Table S5 for economic parameters and assumptions) to determine a
plant gate internal rate of return (IRR) for given product prices, or a plant gate price
of ethylene for a given IRR. The plant gate IRR (in percentage) is required to obtain a
net present value (NPV) of zero for fixed products prices, associated with the pioneer
plant analysis. The plant gate price of ethylene (also called minimum ethylene selling
price [MESP]) is obtained for a zero NPV with a fixed IRR. While the MESP can be used
to assess the marketplace competiveness of a given process, it may not be best
suited for evaluating the proposed strategy because revenues from other coprod-
ucts are significant when compared with those from ethylene sales. In the subse-
quent discussion, we calculate IRR and NPV, along with MESP for comparing process
variations against one another or for performing sensitivity analysis.

RESULTS AND DISCUSSION

Base Case
Material and Energy Balances
The material and energy balances for this process under the base case design (see
Table 2 for the values of key process variables) are shown in Figure 3. 95.1% of
the natural gas feed is converted to desired products, while 79.6% of the energy
input remains in these products. Hydrogen is an important coproduct as 28.6% of
the natural gas feed is converted to H2, and it stores nearly 40.8% of the energy
input. Furthermore, an effective separation and recovery section is essential due
to the low methane one-pass conversion, which results in a methane-rich recycle
stream that is 2.2-fold larger than the natural gas feed.

Joule 2, 349–365, February 21, 2018 355

Figure 3. Block Flow Diagram of Methane Conversion Process
(A and B) Material (A) and energy balances (B) for base case design.

Capital and Operating Costs

The results for the base case design are shown in Table 3. The total installed
equipment cost is estimated to be $635.8 million; the TCI, which includes other
direct and indirect costs, is $1,212.4 million. The catalytic conversion section is
the largest contributor (37.4%) due to the large cost of the high-temperature
reactor.

The total raw material cost is estimated to be 418.2 MM$/yr, and the total operating
cost, which includes both variable and fixed operating costs, is 492.5 MM$/yr. Total
revenues from product sales are 1,188.0 MM$/yr. The process produces significant
amounts of hydrogen, benzene, and naphthalene in addition to ethylene. The corre-
lation between hydrogen prices and natural gas prices is based on a US Department
of Energy report for steam methane reforming technology,69 while the price of ben-
zene is assumed to be linearly correlated with the price of ethylene through their cor-
relations to oil prices (see Figure S5). Historical data show that the accuracy of the
correlation between ethylene price and oil price is more than 95%, and the same
rule applies to benzene with 92% accuracy.70

The cost growth analysis suggests that the TCI for a pioneer plant would be more
than twice (2,461.6 MM$/yr see Table 3) the investment for an nth plant. The total
operating cost for a pioneer plant (568.9 MM$/yr) is slightly higher than that for an
nth plant (492.5 MM$/yr) because the fixed operating costs are calculated based
on the total capital costs. Furthermore, our analysis suggests that the proposed
process will reach 81% capacity after one year and full capacity after three years.
This result is mainly due to the proposed process having only one section (catalytic
conversion) that incorporates unproven technology, while other sections are de-
signed based on the industrial olefins purification process. The subsequent discus-
sion is based on the pioneer plant analysis to avoid routinely overstating any
advantages.

IRR and MESP

If we assume ethylene is sold at its 2015 average market price ($990/MT), the result-
ing IRR is 16.6%, which is slightly lower than the required threshold (20%

356 Joule 2, 349–365, February 21, 2018

Table 3. Total Capital Investment and Operating Cost
Process Section Installed Cost (MM$)
Catalytic conversion 237.8
Compression 111.2
Separation and recovery 24.5
Refrigeration 104.9
Storage 69.7
Power generation 62.4
Utilities 25.3
Total installed equipment cost 635.8
Total (nth plant) 1,212.3
Total (pioneer plant) 2,461.6
Raw Materials and Utilities Operating Cost (MM$/year)
Natural gas feedstock 225.0
Natural gas for heating 72.1
Catalyst cost 31.1
Makeup water 5.4
Chemicals (for boiler and cooling tower) 1.1
Electricity 83.6
Fixed costs (nth plant) 74.2
Fixed costs (pioneer plant) 150.7
th
Total (n plant) 492.5
Total (pioneer plant) 568.9
Products and Credits Sales Credit (MM$/year)
Ethylene 318.0
Benzene 272.5
Crude naphthalene 239.8
Hydrogen 357.6

used by NETL52) for a natural gas to chemicals project. Alternatively, if we use

20% IRR, the resulting MESP is $1,227/MT, which is 23.9% higher than the
2015 average market price of ethylene. Since there are multiple coproducts with
significant sales, the MESP alone may be misleading in estimating the overall eco-
nomic potential. Thus, we next use IRR = 16.6% to evaluate cost and revenue
contribution.

The total production cost is further divided into process section cost per standard
cubic feet (SCF) of natural gas feed (Figure 4). The catalytic reaction section is the
highest contributor ($39.1/SCF, 32.9%), while the feedstock cost is the second high-
est contributor ($22.5/SCF, 18.9%). The next highest cost drivers are the compres-
sion (14.5%) and refrigeration (13.9%) sections. Interestingly, the contribution of
the sections used for recovering products and recycling unconverted methane
(compression, separation and recovery, refrigeration, power generation, and utili-
ties) is 40.9% of the total production cost, which suggests that the design of effective
separation systems is critical for the development of this strategy. Note that while
the highest sales credits are from hydrogen ($35.8/SCF, 30.1%) and ethylene
($31.8/SCF, 26.8%), benzene and naphthalene also contribute significantly ($27.2/
SCF and $24.0/SCF, respectively).

Joule 2, 349–365, February 21, 2018 357

Figure 4. Cost Contribution per Process Section and Revenue Contribution per Product

Discussion
To identify the major drivers of the process, we study the impact of various techno-
logical and economic variables on the process economics. We also quantify the
effect of uncertainty in market conditions.

Methane One-Pass Conversion

First, the sensitivity of the process economics is evaluated with respect to every pair of
methane one-pass conversion (x) and other key process variables, that is, conversion tem-
perature (T), selectivity to major hydrocarbon products (sp), and ethylene selectivity in
major hydrocarbon products (se). For instance, if x and T are selected, the remaining vari-
ables (e.g., sp and se) assume the values of the base case. The discounted cash flow model
(see Table S7) is used to determine the NPV as a function of each pair of investigated vari-
ables. The results of this analysis are shown in Figures 5A–5C. The point denoted by a star
corresponds to the base case. The results suggest that methane one-pass conversion has
the most significant impact on the overall process economics. A one-pass conversion
greater than 40% is likely to lead to a profitable process under average 2015 market pri-
ces of natural gas and ethylene for a wide range of ethylene selectivity values. In contrast,
the impact of the temperature for catalytic conversion is small because our design allows
the recovery of excessive heat for power generation. However, the change in NPV with
respect to coke formation and ethylene selectivity is more modest at low methane
one-pass conversion. For example, a positive NPV cannot be achieved by only improving
ethylene selectivity if the methane one-pass conversion is less than 25%. As noted earlier,
coproduct credits are significant, which explains the large variation in NPV with small
changes in conversion. The modest variation in NPV with respect to selectivity is more
nuanced. Specifically, replacing production of low-value aromatics (benzene and naph-
thalene) with high-value ethylene requires additional consumption of hydrogen and
energy, which leads to decreasing credits from hydrogen and electricity and ultimately
offsets the credits from replacing aromatics with ethylene. It should be noted that the
selectivity values for production of hydrocarbon products and coke formation are critical
to the feasibility and stability of the process. We limited the coke selectivity range
because a copious amount of cokes deposited on the surface of the catalyst would
hamper the scale-up and commercialization of this strategy. Notably, the above results
are consistent with the benchmarks proposed for the OCM technology.22,71–73

By way of comparison, we calculate the MESP as a function of ethylene selectivity and

methane one-pass conversion with fixed conversion temperature and hydrocarbon
products selectivity (Figure 5D). Note that a minimum price of $280/MT is used for

358 Joule 2, 349–365, February 21, 2018

Figure 5. Impact of Key Process Variables on Process Economics
(A–D) Impact of methane one-pass conversion and (A) conversion temperature on NPV, (B) hydrocarbon products selectivity/coke selectivity on NPV,
(C) ethylene selectivity in hydrocarbon products on NPV, and (D) ethylene selectivity in hydrocarbon products on MESP.

benzene to avoid unreasonable values when the ethylene price is lower than $500/
MT. The sensitivity of MESP at low one-pass conversion (less than 40%) is similar to
that of NPV. However, using MESP may be misleading at higher one-pass conversion
due to the variation of ethylene production rate associated with changing conversion
and selectivity; i.e., the NPV per unit of ethylene (correlated to the MESP) may

Joule 2, 349–365, February 21, 2018 359

Figure 6. Impact of Catalyst Cost on Process Economics
(A and B) The NPV as a function of catalyst material cost and space velocity for (A) base case and (B) FeªSiO2 catalyst.

decrease while both NPV and ethylene production rate increase. For example, the
MESP decreases with the increase of ethylene selectivity when methane one-pass
conversion is greater than 65%, while the NPV continues to increase.

Catalyst Cost
The catalyst cost, which depends on catalyst materials, stability, and regenerability, is
a critical driver. Since assessing the impact of these individual factors separately
is challenging, we study how the catalyst cost would affect the economics. In the
base case, we assume the catalyst material cost is $275/kg and the space velocity
is 15 L/gcat/hr based on the studies by Guo et al.49 and Gerceker et al.50 First, we
report on how the catalyst material cost and space velocity affect the NPV of the
base case (Figure 6A). A positive NPV cannot be attained by increasing the space ve-
locity or decreasing the catalyst material cost when methane one-pass conversion is
25%. This plot can be used to evaluate the catalyst developed for the direct methane
conversion. For example, we can obtain a profile (Figure 6B) for the FeªSiO2 cata-
lyst,49 which gives a methane one-pass conversion of 48.1% and ethylene selectivity
of 19.0% at 1,090 C. Note that a space velocity of >20 L/gcat/hr is likely to lead to an
attractive process even if the catalyst material cost increases to $2,000/kg because of
the improvement in methane one-pass conversion.

Furthermore, we study the impact of the variable catalyst cost, which is due to cata-
lyst regeneration. We assume that the base variable (per hour) catalyst cost is 0.015%
of the catalyst installed cost per hour, based on the catalyst loss rate in the NETL
studies for natural gas to liquid fuels systems.52 Then, to account for regeneration,
we increased the variable catalyst cost to up to 25 times this base value. Figure 7
shows that NPV and IRR fall appreciably as the variable catalyst cost increases; if it
is greater than 25 times its base value, the process becomes economically marginal
(13% IRR or less and MESP > $1,400/MT) even with a 48.1% methane one-pass
conversion.49

Natural Gas and Ethylene Prices

We generate a viability envelope (Figure 8A) to determine the natural gas and
ethylene prices that would lead to a given IRR (note that hydrogen and benzene

360 Joule 2, 349–365, February 21, 2018

Figure 7. Impact of Variable Catalyst Cost on Process Viability

prices are assumed to have correlations with natural gas and ethylene prices, respec-
tively). Curves are shown for 15%, 20%, and 25% IRR. An IRR of 15% establishes a
lower bound on acceptable returns given the market risk (uncertainty of natural
gas and ethylene prices), while 25% IRR is often employed due to erosion of IRR be-
tween project conception and implementation. Consequently, market conditions in
the upper left region are prohibitive, while conditions in the lower right region are
favorable.

The average market prices of natural gas and ethylene in 2015 were $2.63/MMBtu
(equivalent to $113/MT) and $990/MT, respectively. For the base case, we see
that the process would not be economically attractive under the majority of market
conditions between 1997 and 2017, except for the 2010–2014 period when natural
gas prices were low and ethylene prices were historically high.

As discussed earlier, improvements in methane one-pass conversion lead to signif-

icant economic benefit. To better understand how such an improvement would
affect the overall economics, we generate a viability envelope for a process employ-
ing a catalytic system that achieves 48.1% methane one-pass conversion with 100%
selectivity to hydrocarbons (Figure 8B).49 Market conditions during 2015–2017
appear to be favorable (average IRR is 23.8%). However, we note that historic prices
show that there is a high probability that the market conditions during the life of the
project (
30 years) will become unfavorable. Nevertheless, the average ethylene
and natural gas prices over a long period seem to offset the risk. This behavior un-
derscores the need for better understanding of the catalytic chemistry and improved
reactor design, so that valuable C2+ products can be obtained without continued re-
action to coke.

The process viability can be further improved if higher ethylene selectivity is

achieved. In Figure S6, we show a viability envelop for a process employing a catalyst
that achieves 48.1% conversion49 and higher ethylene selectivity in major

Joule 2, 349–365, February 21, 2018 361

Figure 8. Impact of Market Conditions on Process Viability
(A and B) Viability envelope for (A) base case and (B) process with 48.1% methane one-pass conversion.

hydrocarbon products of 97%.50 We see that the process would be economically

attractive under the majority of market conditions between 2005 and 2017. This
analysis indicates the requirement for producing higher-value products (ethylene)
after achieving a viable methane one-pass conversion.

Capital Costs and Plant Scale

Capital costs are, in general, subject to significant uncertainty. Additionally there has
been a history of cost growth associated with the construction and operation of first-
of-kind plants.66 Figure 9A illustrates the impact of changes in capital costs using a
viability envelope. The curves correspond to scenarios where the TCI is obtained by
multiplying the TCI of the base case by a multiplier (0.5, 0.75, ., 1.75). Interestingly,
the process remains viable even when TCI is 1.75-fold the TCI of the base case, pro-
vided that the ethylene price is high (>$2,200/MT) and the natural gas price is low
(<$4/MMBtu). The process would become viable under the current market condi-
tions (red triangle in Figure 9A) if TCI is lower than the base case. Based on our
pioneer plant analysis, the main source of capital cost uncertainty is the catalytic
conversion section. In this respect, a detailed design of the catalytic reactors com-
bined with true reaction kinetics and scalability studies would help to remove the
uncertainty in capital requirements.

In general, the cost of chemical facilities can be reduced by exploiting economies of

scale (e.g., construction of large-scale oil refineries and integrated petrochemical
complexes). Accordingly, we study the impact of plant scale on process economics
(Figure 9B). We see that an increase in the natural gas feed rate to 18 MMSCF/hr
would lead to a positive NPV even with 25% methane one-pass conversion. Further
increase of the natural gas feed rate to 21 MMSCF/hr leads to an IRR of up to 20%
and an MESP as low as $950/MT.

CONCLUSIONS
In this paper, we studied strategies for nonoxidative coproduction of ethylene, aro-
matics, and hydrogen from natural gas. Coke formation and methane one-pass con-
version appear to be the major economic drivers. Specifically, coke formation must
be less than 20% and a minimum one-pass conversion to product of 25% should
be achieved for an economically viable process, even under favorable market

362 Joule 2, 349–365, February 21, 2018

Figure 9. Impact of Capital Costs and Plant Scale on Process Economics
(A) Viability envelope in terms of ethylene and natural gas prices for variation of capital costs.
(B) NPV, IRR, and MESP as a function of plant scale (natural gas feed rate).

conditions. The ethylene selectivity is another driver, which can be potentially ad-
dressed by developing catalysts with higher selectivity of ethylene than aromatics
while maintaining high one-pass methane conversion. Our studies suggest that
improvements in catalyst cost and performance can make the strategy less risky.
Potential reduction in the capital requirements are also needed to remove the risk
associated with market volatility.

Modeling and analysis of these nonoxidative process chemistries, and the catalysts
that enable them, will play a pivotal role in the development of these technologies.
We herein developed a flexible framework that allows systematic evaluation of
various alternatives to identify the key technology gaps that must be overcome in or-
der to develop commercially attractive processes. By identifying the key areas for
future research, we hope that our study will help accelerate the development of
direct methane conversion technologies.

EXPERIMENTAL PROCEDURES
Full experimental procedures are provided in Supplemental Information.

SUPPLEMENTAL INFORMATION
Supplemental Information includes Supplemental Experimental Procedures, six fig-
ures, and seven tables and can be found with this article online at https://doi.org/10.
1016/j.joule.2018.01.001.

ACKNOWLEDGMENTS
We thank Duygu Gerceker for helpful discussions on PtSn bimetallic catalysts.

AUTHOR CONTRIBUTIONS
Conceptualization, C.T.M. and K.H.; Methodology, K.H. and C.T.M.; Software, K.H.;
Formal Analysis, K.H.; Investigation, K.H. and C.T.M.; Resources, J.B.M., G.W.H.,
J.A.D., and C.T.M.; Writing – Original Draft, K.H. and C.T.M.; Writing – Review & Ed-
iting, K.H., J.B.M., G.W.H., J.A.D., and C.T.M.; Visualization, K.H. and C.T.M.; Su-
pervision, C.T.M.

Joule 2, 349–365, February 21, 2018 363

DECLARATION OF INTERESTS
The authors declare no competing interests.
Received: September 4, 2017
Revised: November 22, 2017
Accepted: January 2, 2018
Published: January 23, 2018
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