sustainability /
green chemistry
Optimizing Fe-based catalysis
in carbon dioxide hydrogenation
reactions for future synthesis of liquid
hydrocarbons from seawater
DAVID M. DRAB1, DENNIS R. HARDY2, FELICE DIMASCIO3, HEATHER D. WILLAUER4*
*Corresponding author
1. NRC Postdoctoral Research Associate, Materials Science & Technology Division, Code 6300.2, Naval Research Laboratory, 4555 Overlook Avenue, SW, Washington, D.C., USA
2. NOVA Research Inc., 1900 Elkin Street, Alexandria, VA. 22308, USA
3. Naval Reserve Officer P38, Materials Science & Technology Division, Code 6300.2, Naval Research Laboratory, 4555 Overlook Avenue, SW, Washington, D.C., USA
4. Materials Science & Technology Division, Code 6300.2, Naval Research Laboratory, 4555 Overlook Avenue, SW, Washington, D.C., USA
KEYWORDS
Catalysis, carbon dioxide utilization, renewable energy.
ABSTRACT
The current global reliance upon petroleum fuel presents
unique challenges to develop new, sustainable solutions
to address present and future energy demands. This
perspective describes the research efforts at the US
Naval Research Laboratory (NRL) to address basic
research challenges in the capture and utilization of
CO2 from seawater, where contemporaneous work in
this field is cited. Recent work to optimize CO2 extraction
20 from seawater is briefly highlighted, featuring progress
towards the operational scale-up and demonstration of
an integrated process. The bulk of this article focuses on
concurrent research to develop catalysts and test their
performance in the hydrogenation of CO2, where results
in transitioning from a continuous-stirred tank reactor
(CSTR) system to a more modular and scalable fixed-bed
system are detailed. Efforts to further improve and scale-
up fixed-bed systems are also pointed out with respect to
stabilizing catalysts against degradation effects of water
produced in the hydrogenation of CO2.
INTRODUCTION: THE CURRENT AND FUTURE DEMAND
FOR SUSTAINABLE CARBON SOURCES
A
n unmet and direct need to identify renewable
supplies for current and future global energy
demands presents scientists with a grand challenge
to resolve the conventional reliance upon petroleum-based
fossil fuels. The heavy dependence upon volatile foreign
oil markets results in both a strategic and logistical risk for
the US Navy when supplying active battle groups with
needed aviation and marine fuel. One proposed solution is
the synthesis of fuel at sea, where it is envisioned that liquid
hydrocarbon fuels that meet or exceed military specifications
would be produced at or near point-of-use (1). In comparison
with petroleum-derived fuels, higher product quality is
expected from this ground-up synthetic approach further
improving the overall cost of fuel production and distribution
in-theater. Recent strategies by the US Department of
Defense (DOD) to move towards fuel independence include
Chimica Oggi - Chemistry Today - vol. 31(6) November/December 2013
conventional Fischer-Tropsch (FT) synthesis (2) and biomass
processing (3). However, these approaches do not solve
the risks associated with delivering fuel at sea and they
are not sufficiently sustainable with respect to the possible
negative impact to the environment (especially, with the
generation of carbon dioxide (CO2) as a green-house
gaseous byproduct). Thus, alternative synthetic approaches
to producing fuel should be considered for the realization of
long-term, practical solutions for the US Navy.
CARBON DIOXIDE AND HYDROGEN PRODUCTION
FROM SEAWATER: RENEWABLE TOOLS FOR FUELS
CO2 utilization has received much attention by the
scientific community due to its global availability as
a potential carbon feedstock for the production of a
large variety of synthetic commodity precursors such as
dimethylcarbonate, formic acid, methanol, methane,
olefins, paraffins, and polycarbonates (4-6). With respect to
production of synthetic transportation fuels, the utilization
of CO2 as a feedstock could be considered
carbon-neutral since it is removed from the environment
and converted into a liquid hydrocarbon fuel. Upon
combustion of the fuel, carbon dioxide is returned to the
environment to complete the carbon cycle. In recent
years, reports of different technologies designed to capture
CO2 for either sequestration or utilization have included
membranes and traditional amine based systems for
CO2 extraction from air or flue gas (7), biogeneration from
bacterial, algae farms for biomass processing, and water-
gas shift reaction from industrial syngas (8). Considering
these recent innovations to secure CO2 as a carbon source
for fuels and chemical feedstock, it has been accurately
stated by He and co-workers that we live in the age
of carbon(9). NRL has developed a novel approach
for the extraction of CO2 from seawater via a patented
electrochemical acidification process (10-14). By converting
the inorganic carbon as carbonate and bicarbonate
species present in aqueous equilibrium to carbonic acid,
carbon is removed from seawater in the form of CO2 at 92%
efficiency. Since its initial development, this CO2 capture
technology has been scaled-up and demonstrated in Key
West, Florida, where further improvements are ongoing.
Coincidentally, in the same electrochemical cell, hydrogen
is produced with the capture of CO2 in a ratio that is
conducive for the synthesis of hydrocarbons by way of CO2
hydrogenation (CO2:H2 = 1:3).
 sustainability /
green chemistry
CO2 HYDROGENATION BY THERMOCHEMICAL CATALYSIS methane generation (compare 22.2 to 26.0%).
However, in moving the same catalyst to a fixed-bed
Recognizing the CO2 capture system as a carbon reactor, there was a significant increase of unreacted
source for future fuel synthesis, the next step at NRL was CO (compare 47.3 to 11.5%) and a reduced C2-C5+
to identify a viable route to convert captured CO2 into yield (compare 30.5 to 62.4%). However, modification of
value-added hydrocarbons. There have been recent the fixed-bed reactor GHSV by either changing mass of
advances in electrochemical (15), electrocatalytic(16), catalyst and/or flow rate of reactant gases permitted a
and photocatalytic (17) hydrogenation of carbon dioxide, systematic improvement of performance compared to
however, each of these approaches exhibit limitations the original CSTR conditions. For GHSV = 0.000093 L/sg
with respect to low CO2 conversion efficiencies, selectivity (Table 1B, condition b), CO2 conversion increased to
towards lower molecular weight products (e.g., methane, 60% with additional gains in olefin-to-paraffin ratio (O/P)
methanol), and the technologies are prohibitively (compare 5.6 to 4.2 in CSTR) and comparable selectivity
expensive or sensitive for scale-up considerations. Following for methane and C2-C5+ fraction. These results, along with
a more conventional thermochemical approach, it has kinetic and modeling data, suggest a potential route for
been shown that higher molecular weight olefins/paraffins scale-up production with good selectivity for targeted light
can be produced exclusive of oxygenated by-products olefin products which may be further upgraded via well-
with good selectivity for jet fuel fraction sizing (e.g., C9-C16 studied olefin oligomerizaton processing to jet fuel-quality
carbon number) (18,19). Based on previous work by Riedel hydrocarbons. The objective had then shifted to further
and coworkers (20,21), NRL first designed an iron-based improve the CO2 hydrogenation process with respect to
catalyst with Mn and K promoters on alumina support reactor design and catalyst improvements (40).
and sequentially tested its performance in a continuously-
stirred tank reactor (CSTR) for the hydrogenation of CO2
(22-24). Iron-based catalysts are attractive for their low CATALYST MODIFICATION AND PRODUCT UPGRADING
cost, abundance, and good activity for light olefin (C2-C6)
production when reduced first to an iron carbide phase One of the main concerns for CO2 hydrogenation
(25, 26), as opposed to other transition metal catalysts by thermochemical methods is the prevalence
such as those based on Ni (27, 28) or Co (29, 30) that of degradation pathways that reduce catalyst
predominantly favor methane formation under similar performance and product selectivity over time. These
reaction conditions. processes have been extensively reviewed for syngas
The conversion and selectivity to light olefin products is and can include particle attrition, oxidation/sintering
further improved by promoting with metals such as K (31) effects from water, as well as other modes of catalyst
and Mn (32, 33). As similar K/Mn/Fe-based catalyst systems poisoning, to name but a few (41, 42). Costs associated
were found effective for CO2 hydrogenation (34-37), this with catalyst replenishment/recycle and associated
served as a logical basis for investigations conducted at down-time and discontinuity of reactor processes
NRL where we have recently reported a review describing often are prohibitive for scale-up considerations, 21
metal loading effects (38). and in the case of hydrogenation reactions where
An optimal catalyst composition was determined by water is produced as a byproduct. This has certainly
a step-wise building of the Fe-based catalysts with been the case when CO2 rather than CO is utilized
intermittent performance testing (Table 1, A), where as the carbon feedstock.
a catalyst composition of K/Mn/
Fe/-Al2O3 supported catalyst of
8:12:17:100 led to significant gains in
CO2 conversion (over 40%) as well
as improved olefin concentration
and reduced methane generation.
However, for the scale-up of
hydrocarbon production at the point-
of-use applications (e.g., design of a
fuel production ship or platform), it was
determined that the CSTR technology
would be limiting with respect to the
reactor size required for fuel quantities
needed (39). Therefore catalyst
prepared by the same method was
tested in a fixed-bed reactor that
had been modeled computationally
as a modular reactor, at different
gas-hourly space velocities (GHSVs)
to determine the effect of catalyst
packing and flow rate of reactant
Reactor conditions: (A) 1015 g catalyst dispersed in approximately 400 mL of mineral oil (Aldrich) in the CSTR (Parr
gas feed on CO2 % conversion and Instruments), reduced in CO (563 K, 48 h), hydrogenation of CO2 (563 K, 1333 kPa (13.6 atm), GHSV=0.0015 L/sg at
product selectivity (40). Under GHSV a H2:CO2 ratio of 3:1); (B) 20 gram mixture of 80-200 mesh -Al2O3 with K/Mn/Fe-Al2O3 (8:12:17:100 wt%) to obtain
reported space velocities in 9 inch long SS fixed-bed (3/8 inch ID, 1/2 inch OD) reduced with CO at 265 psig and 593
similar to that of the CSTR (GHSV = K for 2 hours and then hydrogenation of CO2 was at 593 K, 1827 kPa (265 psig) with a H2/CO2 ratio of 3:1. The effluent
gas analysis by gas chromatography described in Experimental Sections (23, 40).
0.0015 L/sg, Table1B, condition f),
there were slight improvements to CO2 Table 1. Effects of changing composition of alumina-supported iron-based catalysts on CO2
conversion percent (compare 44.7 to hydrogenation performance in preliminary tests in CSTR (A) and GHSV-optimized fixed-bed
41.4%) as well as olefin/paraffin ratio reactors (B).
(compare 4.6 to 4.2) and reduced

Chimica Oggi - Chemistry Today - vol. 31(6) November/December 2013

 sustainability /
green chemistry
By converting CO2 to an equivalent FT product, an additional
equivalent of water is produced when considering the
combination of reverse water-gas shift (RWGS, Equation 1)
production of CO from CO2 followed by FT conversion of CO
to hydrocarbons (Equation 2) (22).
The persistence of water is considerable overall 3. Mushrush G. W., Beal E. J., et al., Ind. Eng. Chem. Res., 39(10), 3945-
(Equation 3), especially when accounting for the additional
quantities generated when methane is obtained 4. Song C. Catal. Today, 115, 2-32 (2006).
as a byproduct (Equation 4).
(1)
(2)
(3)
(4)
In a recently published article (43) different reduction
conditions (CO versus H2) were tested with the previously
reported Fe-based catalyst either in native form or when
modified by incipient wetness impregnation with silica via
tetraethylorthosilicate (TEOS) precursor.
Previous studies had suggested silica-functionalized
catalysts might be more resilient towards water
degradation due to prevention of supported metal
sintering and agglomeration(44) as well as enhanced
selectivity for light olefins as a result of improved dispersion
of iron and uniform pore structure (45). Our results indicated
a reduction in CO2 % conversion and hydrocarbon
selectivity to olefins by the modification of a Fe/Mn/K
catalyst supported on alumina with TEOS under fixed-
bed conditions. Further, the results indicated that, under
fixed-bed reaction conditions for CO2 hydrogenation,
the Fe/Mn/K catalyst produced lighter olefins in greater
quantities when CO was used as the reducing agent.
22 These observations are supported by Bukur (46, 47) and
others (48-50), where it is found that CO-reduced iron-
based catalysts form a carbide phase considered essential
for chain-growth propagation, and indicate promising
directions for conditions and catalyst compositions to use
in the scale-up demonstration of CO2-to-fuel conversion.
Work is ongoing to improve reactor design as well as
new and improved catalyst compositions and loading
conditions.
CONCLUSIONS AND FUTURE OUTLOOK
Recent advances in the thermochemical route to CO2
hydrogenation suggests a scalable process for the
renewable production of liquid hydrocarbons, but further
investigation is required to optimize the synthetic approach
for practical consideration. Increasing the oligomerization
of light olefin products to higher molecular weight liquid
hydrocarbons remains a key objective, where limitations
currently exist in identifying appropriate reactor conditions
and stable catalysts that can manage the large scale
production cycles needed for future Naval transportation
energy needs. The team at NRL is expanding its synthetic
scope to include new classes of mesoporous catalyst
support materials and different routes to synthesize reactive
metal oxide catalysts which are both high in their conversion
of CO2 and selectivity towards useful hydrocarbon products
(e.g., C2-C5+ olefins). Using both kinetic modeling and
small-scale reactor screening, optimal reactor conditions
and ideal catalyst compositions will identify best candidates
for scale-up in a commercial research reactor unit, 48. Sirmanothan N., Hamdeh H. H., et al., Catal. Lett., 82, 181-191 (2002).
where further improvements will be recommended based
upon data obtained at the larger scale.
Chimica Oggi - Chemistry Today - vol. 31(6) November/December 2013
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