Chemical looping oxidative coupling of methane (CLOCM) is a promising process for direct methane conversion to C 2 products. Under the chemical looping approach, the oxygen carrier that provides lattice oxygen, in place of molecular oxygen, is used for methane oxidation. This study performs redox experiments that probe the C 2 selectivity enhancement properties of a Mg−Mn composite oxygen carrier through the use of a low concentration of Li dopant. It was found that the C 2 selectivity of the Li-doped oxygen carrier in CLOCM is universally higher than that of the undoped Mg 6 MnO 8 oxygen carrier with a maximum improvement in selectivity of ∼50% . Density functional theory simulation reveals that the Li dopant has a short-range effect on the formation of oxygen vacancies. The Li-doping-induced oxygen vacancy reduces the adsorption energy of methyl radicals and increases the C−H activation barrier. These findings provide a catalytic dopant screening strategy for CLOCM, which will substantially enhance the C 2 selectivity with desired oxygen carrier recyclability.
Directly
upgrading natural gas is limited by the stability of its
primary component, methane, and process economics. Since the 1980s,
oxidative coupling of methane (OCM) has shown potential to produce
ethylene and ethane (C2s). The typical OCM approach catalytically
converts methane to C2 products using molecular oxygen,
reducing process efficiency. To overcome this, chemical looping OCM
converts methane to hydrocarbons via intermediate oxygen carriers
rather than gaseous cofed oxidants. The chemical looping approach
for OCM has been studied mechanistically for the first time with a
Mn–Mg-based catalytic oxygen carrier (COC). The COC delivered
stable performance in a fixed bed for 100 cycles for more than 50
h with a 63.2% C2 selectivity and 23.2% yield. These experimental
results and original process simulations of an OCM chemical looping
system for C2 or liquid fuel production with electricity
cogeneration present a direct method for methane utilization.
Syngas is a valuable chemical intermediate
for producing commodity
chemicals, such as olefins, methanol, liquid fuels, etc. The chemical
looping route for syngas production presents an attractive alternative
to state-of-the-art technology, such as partial oxidation, autothermal
reforming, and steam methane reforming. Out of the several chemical
looping configurations, the co-current moving-bed reactor with iron
titanium composite metal oxide particles has demonstrated a high-purity
syngas production. In this study, an alternative reactor configuration
(indirect chemical looping system) is proposed to the co-current moving-bed
reactor system (direct chemical looping system) to enhance the syngas
yield. The indirect chemical looping system consists of a fuel reactor
and a syngas generation reactor, both operated in countercurrent mode,
with respect to the gas–solid flow, as opposed to just one
co-current fuel reactor in the direct chemical looping system. This
unique gas–solid contact pattern in the indirect chemical looping
system aids in greater utilization of CO2 and H2O and improves the thermodynamic performance for syngas production.
Thermodynamic simulations in Aspen Plus software are performed for
system analysis and comparison under isothermal and autothermal conditions.
Isothermal analysis at several different temperatures and pressures,
with and without co-injection of CO2/H2O, is
conducted to explain the behavior of the proposed system. Autothermal
operation of the system under different pressures is also evaluated
to determine the maximum syngas yield within the constraints of a
practical system for syngas production to further produce liquid fuels
via Fischer–Tropsch synthesis. The results from these simulations
are compared against the direct chemical looping system to highlight
the difference in thermodynamic constraints between the two processes.
The oxidation behavior of reduced Fe2O3–MgAl2O4 with CO2 and H2O is experimentally
tested at different pressures and temperatures to gain an understanding
for the syngas generation reactor in the indirect chemical looping
system.
Oxidative coupling of methane (OCM)
is a compelling strategy for
the direct conversion of methane to C2+ hydrocarbons in
order to produce fuels and value-added chemicals. Nevertheless, it
remains challenging to achieve the high C2+ yield that
is desirable in industrial synthesis. Here, a lithium, tungsten-codoped
Mg-Mn based oxygen carrier, (Li,W)-Mg6MnO8,
is prepared for the chemical looping oxidative coupling of methane
(CLOCM) technology. The designed codoped oxygen carrier exhibits an
improved OCM performance with a C2+ yield of 28.6% at 850
°C, which is 80% higher than the combined yields of the single
Li- and W-doped oxygen carriers, and 330% higher than that of the
undoped Mg6MnO8 oxygen carrier. The enhanced
activity has also been demonstrated over 50 redox cycles in the CLOCM
system. In combination with solid characterization, density functional
theory calculations reveal that, as compared to the single-metal-doped
Mg6MnO8, the Li and W codopants work synergistically
which not only enhances CH3 dimerization but also inhibits
CO2 formation. This effect was attributed to the suppressed
formation of unselective oxygen vacancies, which in turn leads to
the C2+ yield enhancement. As a result, (Li,W)-Mg6MnO8 was found to be one of the best performing oxygen
carriers as compared to other oxygen carriers reported in the literature.
These findings provide new insights into the understanding of the
codoping effect on the activity of a Mg-Mn based oxygen carrier for
C2+ production and can open new avenues to design an environmentally
and economically feasible CLOCM system.
Alkanes are potential precursors to many value-added chemicals such as olefins and other petrochemicals. However, the conversion of the light alkanes can be challenging due to their strong C-H bonds....
The transformation of CO 2 to chemicals and fuels offers a means of CO 2 utilization while mitigating the global carbon footprint. An attractive strategy involves the CO 2 reforming of methane with oxygen carriers. In this strategy, methane is used as the reducing agent to provide hydrogen for CO 2 reduction. This study aims to investigate the reactivity of the ilmenite-based oxygen carrier undergoing a redox reaction for CO 2 reduction coupled with methane reforming and the underlying mechanism using combined experimental study and density functional theory calculations. The enhanced activity for the methane conversion and CO 2 reduction with FeTiO 3 was revealed under the CH 4 /CO 2 ratio of >8.75 with CO 2 conversion of >95%. The mechanistic probe indicated that the oxygen vacancies and hydrogen atoms from the successive dissociation of CH 4 are crucial for CO 2 activation and reduction. In the dominant formate pathway, the CO 2 molecule is hydrogenated to the HCOO* intermediate species and then decomposes to CO via the C−O and C−H cleavage at the oxygen vacancy site with a low barrier of 62.5 kJ/mol. These results shed light on the fundamental understanding of hydrogen-assisted CO 2 reduction over ilmenite-based oxygen carries and open up future research on potential strategies to improve CO 2 utilization for redox reactions.
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