Showcasing research from Dr L.-S.

Fan’s group at As featured in:

The Ohio State University (OSU)

Utilization of CO2 as a partial substitute for methane feedstock

in chemical looping methane–steam redox processes for
syngas production

This work describes the unique capability of a chemical looping

system developed at OSU that utilizes CO2 as a feed along with
fossil and/or renewable fuels to produce syngas and subsequent
commodity products such as liquid fuels and methanol without
any CO2 emissions. We present thermodynamic process
simulations and experimental results to showcase this novel
technology.
See Liang-Shih Fan et al.,
Energy Environ. Sci., 2017,
10, 1345.

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Utilization of CO2 as a partial substitute for
methane feedstock in chemical looping methane–
Cite this: Energy Environ. Sci.,
2017, 10, 1345 steam redox processes for syngas production†
Received 20th December 2016,
Accepted 13th February 2017 Mandar Kathe,‡ Abbey Empfield,‡ Peter Sandvik, Charles Fryer, Yitao Zhang,
Elena Blair and Liang-Shih Fan*
DOI: 10.1039/c6ee03701a
rsc.li/ees
This work describes the unique capability of a novel chemical
looping system that utilizes CO2 as a feedstock for methane
reforming. This system uses an iron–titanium composite metal
oxide and a co-current moving bed reactor system to yield a higher
purity of syngas than the conventional CO2 dry reforming system.
1. Introduction
Carbon capture utilization and sequestration (CCUS) is a grand
challenge for modern chemical engineers. Many new techno-
logies strive to implement either CO2 capture or CO2 utilization,
but the two concepts are rarely thought of as mutually
inclusive.1 This work highlights the unique capability of a novel
chemical looping system to co-process CO2 and CH4, which no
current technology is able to achieve in a commercially relevant
way. The novel chemical looping system presented here utilizes
a co-current moving bed gas–solid contact pattern coupled with
iron–titanium composite metal oxide (ITCMO) carriers for high
purity syngas generation through the co-processing of H2O,
CO2 and CH4. To comprehend the novelty of this chemical
looping based CO2 utilization technology, it is first paramount
to identify fundamental limitations in existing commercial
scale technologies utilizing CO2 and CH4 for syngas produc-
tion. A critical survey of the existing conceptual technologies,
including dry reforming, mixed reforming and tri-reforming,
can aid in understanding the fundamental limitations of each
of these technologies that have prevented them from achieving
commercialization.2–4
Dry reforming oxidizes CH4 using CO2 as a soft oxidant.3 The
conversion of 1 mole of CO2 to CO is required for the oxidation
of 1 mole of CH4. This limits the possible H2 : CO ratio to a
Ohio State University, Department of Chemical and Biomolecular Engineering,
Columbus, Ohio, USA. E-mail: fan.1@osu.edu
† Electronic supplementary information (ESI) available: Supplementary material
provides details on heat balance computations, experimental setup and case
studies for CRP 4 1. See DOI: 10.1039/c6ee03701a
‡ Co-first authors.
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Broader context
The utilization of CO2 as a feedstock in a chemical looping process that
converts methane to syngas and a variety of downstream products has the
ability to be impactful in the field of carbon capture, utilization, and
sequestration (CCUS). The Ohio State University Chemical Looping
methane to syngas (MTS) process that involves injection to the reducer
of both the fresh CO2 and recycled CO2 produced from downstream
syngas conversion processes drastically reduces methane or natural gas
usage. This paper shows that the MTS technology can be a commercially
viable solution for synergistic CO2 capture and utilization as a feedstock
to produce carbonaceous products in a process system without CO2
emission. This thermodynamic feasibility is driven by the synergy of
using lattice oxygen and vacancies from iron oxides enabling high
efficiency conversion of CO2 to CO. Its integration into a commercial
gas to liquids (GTL) plant is illustrated as a demonstrative example to
describe the important role of CO2. The experimental data compare well
with the results from the thermodynamic model simulation. The overall
process simulation shows significant economic advantages for integra-
tion of the experimentally verified thermodynamic results on a commer-
cial scale (50 000 barrel per day) GTL plant.
maximum of 1 : 1, which prohibits integration into some desir-
able downstream processes. Additionally, the endothermic heat
necessary to sustain the reaction is supplied by combustion of
CH4 with air, hampering the net carbon efficiency. Mixed
reforming with H2O and CO2 can overcome the limitations of
carbon deposition common in dry-reforming technologies and
increase the H2 : CO ratio beyond 1 : 1.4 However, the reactions
of steam and CO2 with methane are endothermic and require
the combustion of CH4 with air to satisfy the endothermic heat
requirements of the reaction. Another class of mixed reforming
utilizes O2 instead of H2O. The partial oxidation of CH4 with O2
can offset the endothermic heat requirements of CO2 with CH4
and provide an overall heat neutral reaction, but the addition
of O2 results in H2 : CO ratios lower than dry reforming. Tri-
reforming is a synergistic combination of endothermic CO2 and
H2O reforming and exothermic partial and complete oxidation
of CH4 with O2.2 The intricate integration of various reactants
to produce syngas is thermodynamically feasible, and it gives
Energy Environ. Sci., 2017, 10, 1345--1349 | 1345

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the desired H2 : CO ratios for downstream applications. However,
thermodynamics shows a high sensitivity of the syngas product
composition on the reactant mixture ratios. This sensitivity
necessitates precise control of the relative ratios of CH4 : CO2 :
H2O : O2 during the reactions in the system. Commercial tri-
reforming is inhibited by the difficulty of maintaining these
precise ratios at every point on the catalyst surface.
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Novel chemical looping process
The novel chemical looping system presented here overcomes the
challenges of low H2 : CO ratios, the need for external CH4
combustion to satisfy energy requirements, and sensitivity of the
reactant composition of the catalyst surface, which are limitations
of the current conceptual technologies. Chemical looping is able to
overcome low H2 : CO ratios in a similar manner as tri-reforming
by reacting CH4 with H2O, CO2, and oxygen. The distinction
between the two reaction schemes is that chemical looping
uses a metal oxide oxygen carrier, specifically ITCMO, therefore
eliminating the need for an air separation process.
Chemical looping utilizes two reactors as shown in Fig. 1.
The first is a reducer reactor where CH4 is partially oxidized to
syngas by CO2, H2O, and the donation of lattice oxygen from
ITCMO. The lattice oxygen lost by ITCMO in the reducer reactor
is replenished in the combustor, the second reactor, using air.
The overall reaction in the reducer is endothermic, and the
overall reaction in the combustor is exothermic. The decoupling
of the endothermic and exothermic processes is uniquely
exploited to satisfy the energy requirements of the system. The
following sections address the novelty of choosing ITCMO and a
co-current moving bed in a chemical looping system.
Why ITCMO?
Utilizing lattice oxygen from ITCMO instead of molecular oxygen
yields thermodynamic stability benefits by offering a wide and stable
region for operation. In addition to classical thermodynamics based
motivation (detailed in Section 2), considerations on scientific
molecular level investigations and bulk recyclability based investiga-
tions are used as decision making tools for choosing ITCMO and to
determine an optimal composition for ITCMO. The molecular level
scientific investigations include computing ionic diffusion lattice
oxygen using a combination of micro-scale experiments and density
functional theory calculations.5–7 The bulk recyclability (experi-
mental investigations on maintaining reactivity for 1000 redox
cycles) and maintenance of a normal crushing strength of
particles during the 1000 redox cycles are simple, yet powerful
Fig. 1 MTS chemical looping system for high quality syngas production.6
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criteria which served as the ultimate screening criteria in
addition to classical thermodynamics and molecular level
scientific investigations.5–7
Why a moving bed reducer?
Given the thermodynamic motivation, the first aspect of design
consideration is to determine a gas–solid contact mode for the
reactors that can overcome the challenges for gas–solid mixing
described for the tri-reforming technology. Two possible gas–
solid contact modes for the reactor are considered, a co-current
moving bed reactor and a fluidized bed reactor.5 Both reactor
systems can be optimized to reaction conditions that favor
partial oxidation by adjusting the stoichiometric ratio of metal
oxide to fuel. Under identical stoichiometric conditions, a
co-current moving bed system and a fluidized bed system will
yield different thermodynamically favored products. Solid particles
such as ITCMO used in a fluidized bed for a continuous operation
are of mixed residence time with mixed oxidation states at the
outlet of the reactor. In contrast, a co-current moving bed reactor
for a continuous operation will exhibit a single oxidation state
corresponding to a single residence time at the outlet of the
reactor. For the reducer reactor, a co-current moving bed system
can selectively synchronize its operation to the designed thermo-
dynamic operating conditions, while a fluidized bed cannot. The
motivation for utilizing a co-current moving bed in-conjunction
with ITCMO over a fluidized bed is further solidified using a
combination of hydrodynamic pressure balance investigations,8
optimization of mixing characteristics and proof of concept
experiments.5,9
2. Thermodynamics: comparing
tri-reforming to chemical looping for
CO2 co-utilization with CH4
The thermodynamics in terms of Gibbs free energy minimiza-
tion (using the RGIBBS module in ASPEN PLUS v8.8) of a tri-
reforming system are compared to a co-current moving bed
MTS system in Fig. 2. The variables of interest include the
Fe2O3 : C molar ratio, the H2O : C molar ratio and the CO2 : C
molar ratios. These variables are initially analyzed under iso-
thermal conditions to identify the set of input conditions for
maximum syngas production from 1 kmol h 1 of CH4. It is seen
that CH4 conversion is greater than 98% at 1000 1C and 5 atm
for [O]/CH4 ratios that are greater than 1 for both molecular
oxygen and the ITCMO system.
Lattice oxygen from ITCMO (FeTiyOx) is theoretically able to
achieve a syngas yield of B2.7 moles syngas per mole CH4, over a
wide range of [O]/CH4 values (1.5–4), due to the thermodynamic
favorability of the oxygen carrier to remain at the FeTiO3 oxida-
tion state rather than over oxidizing the syngas to CO2. Molecular
O2 does not have additional thermodynamically favorable oxida-
tion states and therefore lacks the flexibility that is observed
when ITCMO is used as the oxygen carrier.
It can be seen from Fig. 2 that at yields of B2.7 moles syngas
per mole CH4, the ITCMO particle performance is comparable
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Fig. 2 Comparison of molecular O2 and ITCMO particle syngas yields at Fig. 4 H2 : CO ratio for the tri-reforming system and the ITCMO system
1000 1C and 5 atm. for a [O] : CH4 ratio of 1.2 at 1000 1C, 5 atm.

to peak molecular O2 syngas yields, but with the added benefit of

being able to operate at a wider range of [O]/CH4 values (1.5–4).
This is further explained by considering the [O]/CH4 ratios of 1.2
and 2.4 for both systems and applying CO2 and H2O injection at
1000 1C and 5 atm to investigate the syngas generation perfor-
mance. Fig. 3a shows the syngas yield for the ITCMO system
while Fig. 3b shows the syngas yield from a tri-reforming system
at [O]/CH4 ratios of 1.2 and 2.4, respectively.
The ITCMO yields a maximum syngas production of 3.25
moles H2 + CO for a [O]/CH4 ratio of 1.2, which drops to 3.1 for
a [O]/CH4 of 2.4. The corresponding values for a molecular
oxygen system yield 2.8 and 1.4 for the molecular O2 system.
For an isothermal analysis, the advantages of using ITCMO Fig. 5 Pictorial representation of approaches for adiabatic modelling of a
particles over molecular O2 for CH4 reforming are thus evident chemical looping system.5,9,10
when considering the co-injection of H2O and CO2.
designed to find a synergistic balance between the endo-
Considerations on heat balance based auto-thermal design
thermic dry reforming and steam reforming reactions, and
The heat duty considerations are demonstrated by considering the exothermic methane partial and complete oxidation reac-
a H2 : CO molar ratio of 2.19, which is typically suitable for a tions. The chemical looping reducer is designed to have FeTiO3
cobalt-based Fischer–Tropsch catalyst. Fig. 4 shows the H2 : CO to be in equilibrium with the syngas produced from methane.
ratio variation for the molecular O2 and ITCMO systems, The minimum TiO2 to Fe2O3 molar ratio for simulating the
investigated in Fig. 3. The plane that intersects the H2 : CO appropriate ITCMO chemistry is 2 : 1. For TiO2 to Fe2O3 molar
ratio of 2.19 is shown. The points of intersection are quantified ratios that are higher than 2 : 1, on an isothermal basis, the
for their H2 + CO flow rates and the net heat duty to gain insight chemistry remains the same.9
into heat balance considerations for the molecular O2 and
the ITCMO system. The molecular oxygen system is typically

Fig. 6 Net heat duty (Gcal h 1) vs. syngas yield (mol H2 + CO produced
Fig. 3 Comparison of syngas production per mole of CH4 at 1000 1C and per mol of CH4) for a [O] : CH4 ratio of 1.2 at 1000 1C, 5 atm; (Fig. S1: the
5 atm; (left) ITCMO, and (right) molecular O2. case for a [O] : CH4 ratio of 2.4 is given in the ESI†).

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The optimal amount of support is determined by heat
balance considerations for sustaining autothermal operation
of the chemical looping system. Fig. 5 shows the overall
methodology used in completing the adiabatic simulation, with
further details given in the ESI.†5,9,10
Fig. 6 shows the net heat duty of the molecular O2 and
ITCMO system at a temperature of 1000 1C and 5 atm as a
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function of the syngas yield (H2 + CO). Note that a [O] : CH4 ratio
of 1.2 corresponds to the peak thermodynamic condition given
in Fig. 2 for the molecular O2 based tri-reforming system. The
ITCMO system is able to yield a higher syngas at the appro-
priate H2 : CO ratio (2.19) while satisfying the heat balance
conditions at the same [O] : CH4 ratio.
3. MTS-GTL process for 50 000 bpd
GTL with CO2 co-injection
The novel chemical looping process cannot simply be better
than conceptual processes including tri-reforming, it must be
competitive with the current commercial scale syngas genera-
tion technologies. There are a range of applications for syngas,
one such application that is focused on here is use in a gas to
liquids process (GTL) using a cobalt based F–T catalyst.
Conventional commercial scale GTL technologies use auto-
thermal reforming (ATR) to produce syngas. The auto-thermal
reformer uses an air-separation unit to provide molecular oxygen
and steam to convert natural gas and recycled fuel gas to the
desired syngas specifications. A pre-reformer is used to crack
heavier hydrocarbons in natural gas and recycle fuel gas before
the gas stream enters the auto-thermal reformer. As shown in
Table 1, the baseline ATR-GTL plant utilizes 19 849 kmol h 1 of
natural gas to produce 50 000 bpd of liquid fuel.11 On an
equivalent normalized basis for this plant, 1 kmol h 1 of natural
gas, and 0.76 kmol h 1 of steam input produces syngas contain-
ing 2.28 kmol h 1 of H2 with a H2 : CO molar ratio of 2.19. The
input also contains an additional fuel gas stream (1.17 kmol h 1),
recycled from downstream processing. The MTS process using
ITCMO is designed to meet equivalent H2 and CO yields with a
Table 1 MTS process system variables for minimum natural gas flow rates for varying steam and CO2 co-injection flow rates (all values normalized to
19 849 kmol h 1)
Baseline case with syngas generation from an ATR system (H2 : CO molar ratio = 2.19) with all flows in kmol h
Natural gas Steam input H2 in syngas
1 0.76 2.28
Chemical looping MTS process using ITCMO (T = 900 1C, P = 1 atm) (H2 : CO molar ratio = 2.19) with all flows in kmol h
CO2 in Natural gas Steam input
0 0.85 0.25
0.151 0.77 0.624
0.176 0.77 0.697
Absolute savings
Natural gas cost
Reduction in natural gas flow
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minimal natural gas feed while maintaining all other down-
stream process variables constant. Optimal operating condi-
tions that satisfy auto-thermal heat balance show that B15%
reduction in natural gas flow is achievable for the MTS system
with steam and natural gas co-injection. In the case when CO2
is used as a partial substitute for natural gas, a maximum
reduction in natural gas of B23% over the baseline is possible.
On an absolute basis, this corresponds to a natural gas flow
into the MTS system of 15 300 kmol h 1 for production of
50 000 bpd of liquid fuels. At a natural gas price of $2/MMBtu,
the reduction of the natural gas flow by 4549 kmol h 1 (23%
for 50 000 bpd liquid fuels) translates to annual savings of
$59.2 million for the MTS plant when it is operated at 90%
capacity. Such a drastic reduction purely in natural gas flows,
in a commercially relevant manner may be economically dis-
ruptive to the liquid fuel market.
The utilization of CO2 as the reducer feed stock is described
further by the CO2 reaction parameter (CRP) value defined as
(CO2)feedstock/(CO2)syngas. When the value of CRP is greater than
1, the feedstock CO2 to the reducer may come in part from
the recycled stream along with fresh CO2 make-up. A value of
CRP greater than 1 corresponds to a CO2 negative reducer
operation condition that is necessary for the realization of a
CO2 negative process system. In a CO2 negative process, the
MTS process is able to utilize more CO2 than is being generated
in the entire GTL process. The analysis in Table 1 corresponds
to conditions where CRP = 0.92. Cases and methodology
for designing conditions such that CRP is greater than 1 are
presented in the ESI.†
4. Experimental verification of reducer
performance
Experiments have been performed to verify that the reducer can
perform the functions as indicated in the simulation results.
The details of the experimental apparatus may be found in the
ESI.† The experimental conditions are presented in Table 2.
There are five parameters that can be used to evaluate the
1
CO in syngas Nat gas flow
1.04 19 849
1
Fe2O3 input H2 in syngas CO in syngas
0.85 2.281 1.04
0.85 2.281 1.04
0.85 2.282 1.04
$2.5/MMBTU to $6/MMBTU
1
19 849 15 300 = 4549 kmol h
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Table 2 Experimental conditions and results of a bench unit 5. Conclusions

Exp1 Th1 Exp2 Th2 Exp3 Th3 Dramatic reductions in natural gas flows over existing commercial
Input conditions technologies, using Gibbs free energy minimization based motiva-
CH4 (slpm) 0.7 0.7 1.2 1.2 1.1 1.1 tion and experimental verification are illustrated in this study.
H2O/CH4 0.88 0.88 0 0 0 0
CO2/CH4 0.15 0.15 0.15 0.15 0.3 0.3 Simulations indicate that the MTS system is thermodynamically
Fe2O3/CH4 0.81 0.81 0.81 0.81 0.83 0.83 suited to leverage large scale utilization of CO2 in conjunction with
Temp. (1C) 1035 1035 1039 1039 1039 1039
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a carbonaceous feedstock. This study substantiates the crucial role

Output results of the synergy between the lattice oxygen in metal-oxides and
% CH4 conv. 92.6 100 89.8 100 92.3 100 feedstock CO2 reactions that enable a high efficiency conversion of
H2 : CO 2.06 2.23 1.50 1.64 1.40 1.45 CO2 to CO. This synergy ascertains the effective utilization of CO2
CO/CO2 13.5 6.11 11.4 12.8 13.5 12.8
CRP 1.70 0.93 1.05 1.81 2.48 3.19 in the form of a fresh feed and/or downstream recycling in the
% Syngas 95.4 95.2 94.3 97.1 95.2 96.9 methane conversion process to syngas and liquid fuels.

performance of CO2 utilization in the reducer including
methane conversion, H2 : CO molar ratio, CO : CO2 molar ratio,
carbon-dioxide reaction parameter (CRP), and syngas purity on
a dry basis. The calculated results are shown in Table 2. ‘‘Exp’’
represents results from experiments and ‘‘Th’’ represents results
from thermodynamic calculations. Comparing the experimental
values to the thermodynamic calculation values for the output
conditions for all cases indicates a general matching of the
values. The matching indicates that the outlet condition at the
co-current moving bed reducer is close to the thermodynamic
equilibrium condition for the reactions involved. A small devia-
tion of the values could be caused by insufficient residence time
of CH4, resulting in the incomplete conversion of methane in all
experiments. The low CH4 conversion leads to the deviations of
other parameters. As indicated in Table 2, the CRP for some
experiments are considerably larger than 1. Overall, the reason-
able agreement of the thermodynamic and experimental values
substantiates the feasibility of the CO2 negative reducer opera-
tion and hence the CO2 negative process concept as simulated
for chemical looping technology applications. Additionally, the
values of the H2 : CO molar ratio under different conditions show
the flexibility of the CO2 negative reducer operation to mani-
pulate feedstock composition and syngas quality.
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