April 7, 2014
US Navy 'game-changer': converting
seawater into fuel
by Mathieu Rabechault
Washington (AFP) - The US Navy believes it has finally worked out
the solution to a problem that has intrigued scientists for
decades: how to take seawater and use it as fuel.
The development of a liquid hydrocarbon fuel is being hailed as "a
game-changer" because it would signficantly shorten the supply
chain, a weak link that makes any force easier to attack.
The US has a fleet of 15 military oil tankers, and only aircraft
carriers and some submarines are equipped with nuclear propulsion.
All other vessels must frequently abandon their mission for a few
hours to navigate in parallel with the tanker, a delicate
operation, especially in bad weather.
The ultimate goal is to eventually get away from the dependence on
oil altogether, which would also mean the navy is no longer
hostage to potential shortages of oil or fluctuations in its cost.
Vice Admiral Philip Cullom declared: "It's a huge milestone for
"We are in very challenging times where we really do have to think
in pretty innovative ways to look at how we create energy, how we
value energy and how we consume it.
"We need to challenge the results of the assumptions that are the
result of the last six decades of constant access to cheap,
unlimited amounts of fuel," added Cullom.
"Basically, we've treated energy like air, something that's always
there and that we don't worry about too much. But the reality is
that we do have to worry about it."
US experts have found out how to extract carbon dioxide and
hydrogen gas from seawater.
Then, using a catalytic converter, they transformed them into a
fuel by a gas-to-liquids process. They hope the fuel will not only
be able to power ships, but also planes.
That means instead of relying on tankers, ships will be able to
produce fuel at sea.
- 'Game-changing' technology -
The predicted cost of jet fuel using the technology is in the
range of three to six dollars per gallon, say experts at the US
Naval Research Laboratory, who have already flown a model airplane
with fuel produced from seawater.
Dr. Heather Willauer
Dr Heather Willauer, an research chemist who has spent nearly a
decade on the project, can hardly hide her enthusiasm.
"For the first time we've been able to develop a technology to get
CO2 and hydrogen from seawater simultaneously, that's a big
breakthrough," she said, adding that the fuel "doesn't look or
smell very different."
Now that they have demonstrated it can work, the next step is to
produce it in industrial quantities. But before that, in
partnership with several universities, the experts want to improve
the amount of CO2 and hydrogen they can capture.
"We've demonstrated the feasibility, we want to improve the
process efficiency," explained Willauer.
Collum is just as excited.
"For us in the military, in the Navy, we have some pretty unusual
and different kinds of challenges," he said.
"We don't necessarily go to a gas station to get our fuel, our gas
station comes to us in terms of an oiler, a replenishment ship.
"Developing a game-changing technology like this, seawater to
fuel, really is something that reinvents a lot of the way we can
do business when you think about logistics, readiness."
A crucial benefit, says Collum, is that the fuel can be used in
the same engines already fitted in ships and aircraft.
"If you don't want to re-engineer every ship, every type of
engine, every aircraft, that's why we need what we call drop-in
replacement fuels that look, smell and essentially are the same as
any kind of petroleum-based fuels."
Drawbacks? Only one, it seems: researchers warn it will be at
least a decade before US ships are able to produce their own fuel
Comment from article:
The latest "German" Submarines before the end of the war were
using seawater and peroxide as fuel, and were as efficient as if
not more than nuclear according to Vladamir Terzisky, the
Bulgarian born Engineer. Check out his youtube videos.
[ Hydrogen Peroxide / Seawater ]
EXTRACTION OF CARBON DIOXIDE AND HYDROGEN
FROM SEAWATER AND HYDROCARBON PRODUCTION THEREFROM
Also published as: US2011281959 // WO2011142854 //
Apparatus for seawater acidification including an ion
exchange, cathode and anode electrode compartments and
cation-permeable membranes that separate the electrode
compartments from the ion exchange compartment. Means is provided
for feeding seawater through the ion exchange compartment and for
feeding a dissociable liquid media through the anode and cathode
electrode compartments. A cathode is located in the cathode
electrode compartment and an anode is located in the anode
electrode compartment and a means for application of current to
the cathode and anode is provided. A method for the acidification
of seawater by subjecting the seawater to an ion exchange reaction
to exchange H+ ions for Na+ ions. Carbon dioxide may be extracted
from the acidified seawater. Optionally, the ion exchange reaction
can be conducted under conditions which produce hydrogen as well
as carbon dioxide. The carbon dioxide and hydrogen may be used to
RECOVERY OF [CO2]T FROM SEAWATER/AQUEOUS
BICARBONATE SYSTEMS USING A MULTI-LAYER GAS PERMEABLE MEMBRANE
The present invention is generally directed to a system for
recovering CO2 from seawater or aqueous bicarbonate solutions
using a gas permeable membrane with multiple layers. At elevated
pressures, gaseous CO2 and bound CO2 in the ionic form of
bicarbonate and carbonate diffuse from the seawater or bicarbonate
solution through the multiple layers of the membrane. Also
disclosed is the related method of recovering CO2 from seawater or
aqueous bicarbonate solutions.
METHOD FOR THE CONTINUOUS RECOVERY OF
CARBON DIOXIDE FORM ACIDIFIED SEAWATER
A method for recovering carbon dioxide from acidified seawater
using a membrane contactor and passing seawater with a pH less
than or equal to 6 over the outside of a hollow fiber membrane
tube while applying vacuum or a hydrogen sweep gas to the inside
of the hollow fiber membrane tube, wherein up to 92% of the
re-equilibrated [C02]T is removed from the natural seawater.
CATALYTIC SUPPORT FOR USE IN CARBON DIOXIDE
A catalyst support which may be used to support various catalysts
for use in reactions for hydrogenation of carbon dioxide including
a catalyst support material and an active material capable of
catalyzing a reverse water-gas shift (RWGS) reaction associated
with the catalyst support material. A catalyst for hydrogenation
of carbon dioxide may be supported on the catalyst support. A
method for making a catalyst for use in hydrogenation of carbon
dioxide including application of an active material capable of
catalyzing a reverse water-gas shift (RWGS) reaction to a catalyst
support material, the coated catalyst support material is
optionally calcined, and a catalyst for the hydrogenation of
carbon dioxide is deposited on the coated catalyst support
material. A process for hydrogenation of carbon dioxide and for
making syngas comprising a hydrocarbon, esp. methane, reforming
step and a RWGS step which employs the catalyst composition of the
present invention and products thereof.
1. Technical Field
 The present invention relates to the field of catalysts for
hydrogenation of carbon dioxide. In particular, the present
invention relates to supported catalysts for hydrogenation of
carbon dioxide wherein the catalyst support is coated with a
material capable of catalyzing a reverse water-gas shift reaction.
 2. Background Art
 Increasing awareness of the environmental impact of carbon
dioxide (C02) emissions has lead to an immense increase in
research and development efforts to bind C02. Proposals range from
capturing C02 directly from the flue gas emitted by heavy industry
or from the atmosphere by binding it in inorganic oxides. Avalos-
Rendon, et al., Journal of Physical Chemistry A 113, 6919 (2009)
and Nikulshina, V., et al., Chemical Engineering Journal 146 (2),
244 (2009). One approach is to reduce the C02 over catalysts, to
convert it to more valuable hydrocarbons using photochemical,
electrochemical or thermochemical processes.
 Electrochemical and photochemical C02 conversion is still
in its infancy and at present has major drawbacks. Photocatalysts
tend to require a sacrificial electron donor. Collin, J. P. and
Sauvage, J. P., Coordination Chemistry Reviews 93 (2), 245 (1989)
and Fujita, E., Hayashi, Y., Kita, S., and Brunschwig, B. S.,
Carbon Dioxide Utilization for Global Sustainability 153, 271
(2004). Further, neither photocatalytic nor electrocatalytic
conversion of C02 yield long chain hydrocarbons nor do they show
very high C02 conversion efficiencies. Noda, H. et al., Bulletin
of the Chemical Society of Japan 63 (9), 2459 (1990).
 Thermochemical C02 conversion, in contrast, has been known
for several decades and is presently the most proven and
successful approach to producing hydrocarbons (HC) above methane
at high conversion yields. Russell, W. W. and Miller, G. H.,
Journal of the American Chemical Society 72 (6), 2446 (1950) and
Dorner, R. W., Hardy, D. R., Williams, F. W., and Willauer, H. D.,
Applied Catalysis A: General (2009). This research is primarily
driven by the U.S. military's significant demand for jet fuel and
the associated target of increasing energy independence and
battlefield readiness as well as reducing C02 emissions, in light
of the impending introduction of the cap-and-trade system. One can
envisage a process leading to jet fuel, where the needed carbon
source is obtained by harvesting C02 dissolved in the ocean
(primarily in the form of bicarbonate) and hydrogen through the
electrolysis of water. Willauer, H.D., et al., Energy & Fuel
23, 1770 (2009) and Willauer, H.D., et al., "Effects of Pressure
on the Recovery of C02 by phase Transition from a Seawater System
by Means of Multilayer Gas Permeable Membranes", J Phys Chem A, in
press (2009). C02 and H2 can subsequently be reacted over a
heterogeneous catalyst to form hydrocarbons of desired chain
length and type.
 A key problem with this scenario is the low conversion
yield of C02 hydrogenation processes. Thus, a significant increase
in the conversion yield of C02 hydrogenation catalysts will
enhance the feasibility of the above-mentioned process.
 The target of achieving a high yield, high selectivity
process for C02 hydrogenation to jet fuel can be achieved by use
of a two step synthesis process, involving initial C02/H2
conversion to olefins and subsequent oligomerization over a solid
acid catalyst to jet fuel. Even when using syngas (CO/H2), direct
synthesis of jet fuel is limited by Anderson-Schulz-Flory (ASF)
kinetics to a selectivity of around 50%. However, this type of
selectivity can only be achieved when employing a catalyst that
exhibits an extremely high chain growth probability of 0.9, which
in C02 hydrogenation has not been observed before. Van der Laan,
G. P. and Beenackers, A., Catalysis Reviews-Science and
Engineering 41 (3-4), 255 (1999). Consequently, a two-step process
is advantageous in comparison to the direct route to jet-fuel.
 A conversion of 41.4% of C02/H2 over a K/Mn/Fe catalyst
supported on alumina and an olefin/paraffin ratio of 4.2 has been
reported. Dorner, R. W., Hardy, D. R., Williams, F. W., and
Willauer, H. D., Applied Catalysis A: General (2009). Initial
tests on a cobalt-based catalyst yielded predominantly methane
(CH4), with no carbon monoxide (CO) detected in the product
effluent. Dorner, R. W. et al., Energy Fuels 23 (8), 4190 (2009).
 The conversion of C02 to long chain hydrocarbons has been
established to go through a 2-stage reaction mechanism over iron
catalysts, with initial conversion of C02 to CO on the iron's
magnetite phase (Lox, E. S. and Froment, G. F., Industrial &
Engineering Chemistry Research 32 (1), 71 (1993)), followed by
chain growth as observed in Fischer-Tropsch (FT) synthesis on iron
carbide surface species. Riedel, T., et al., Industrial &
Engineering Chemistry Research 40 (5), 1355 (2001); Bukur, D. B.,
et al., Journal of Catalysis 155 (2), 366 (1995); Herranz, T. et
al., Applied Catalysis a-General 311, 66 (2006); and Li, S. Z. et
al., Journal of Catalysis 206 (2), 202 (2002).
 In cobalt-systems however, the predominant reaction seems
to be C02 conversion directly to methane due to cobalt's limited
water-gas shift (WGS) activity. Based on this model, the approach
within entails the development of a bifunctional catalyst that
includes both reverse water-gas shift (RWGS) activity as well as
FT chain growth activity on the catalyst's surface. The addition
of a second, separate reverse water gas shift (RWGS) catalyst to a
cobalt Fischer-Tropsch catalyst within the same reactor would not
suffice in achieving C02 conversion to long chain HC, as due to
thermodynamic restrictions the carbon monoxide's partial pressure
within the reactor would remain too low and insufficient to
establish an FT regime. Riedel, T. et al., Applied Catalysis
A-General 186 (1-2), 201 (1999).
 It is known, that the RWGS reaction can take place over
promoted ceria at modest temperatures, with an equilibrium
constant of 16% reported over a Pd/Ce02 catalyst at 300 [deg.]C
and an equimolar C02: H2 feed. Pettigrew, D. J., Trimm, D. L., and
Cant, N. W., Catalysis Letters 28 (2-4), 313 (1994). However, if
one replaced palladium with iron, a lower equilibrium constant can
be expected, as iron catalyses the RWGS to a lesser extent than
palladium does. Hilaire, S. et al., Applied Catalysis A-General
258 (2), 269 (2004).The RWGS takes advantage of ceria' s oxygen
storage ability, involving the redox process over the
Ce<4+>/Ce<3+> couple. It has been proposed that the
reaction proceeds via reduction of Ce02 by hydrogen to Ce203,
producing water in the process. Subsequently C02 can then be
expected to re-oxidize Ce203, restoring the initial Ce02 species
and yielding CO. Pettigrew, D. J., Trimm, D. L., and Cant, N. W.,
Catalysis Letters 28 (2-4), 313 (1994). Rates are however
partially limited by H20 re-oxidizing Ce203. Hilaire, S. et al.,
Applied Catalysis A-General 258 (2), 269 (2004). The addition of
base metals to ceria is known to be beneficial for the RWGS, by
reducing the activation energy and increasing the reducibility of
ceria. Li, K., Fu, Q., and Flytzani-Slephanopoulos, M., Applied
Catalysis B -Environmental 27 (3), 179 (2000).
 In WO 96/06064 Al a process for methanol production is
described, which comprises a step of converting part of the carbon
dioxide contained in a feed mixture with hydrogen to carbon
monoxide, in the presence of a catalyst that can be used for the
WGS reaction; exemplified by Zn- Cr/alumina and Mo03/alumina.
 WO 2005/026093 Al discloses a process for producing DME,
which comprises a step of reacting carbon dioxide with hydrogen in
a RWGS reactor to provide carbon monoxide, in the presence of a
supported catalyst selected from ZnO; MnOx (x=l~2); an alkaline
earth metal oxide and NiO.  EP 1445232 A2 discloses a
(reverse) water gas shift reaction for production of carbon
monoxide by hydrogenation of carbon dioxide at high temperatures,
in the presence of a Mn- Zr oxide catalyst.
 A drawback of the known process as disclosed in US
2003/0113244 Al is the selectivity of the catalyst employed; that
is no long chain hydrocarbons are formed. Energy intense
conversion of C02 to CO has to occur prior to upgrading, in a
separate reactor.  The object of the present invention is
therefore to provide a catalyst that shows improved selectivity
and yield in reducing carbon dioxide with hydrogen, with only very
little methane formation, and with good catalyst stability.
Disclosure of Invention
 In a first aspect, the present invention relates to a
catalyst support which may be used to support various catalysts
for use in reactions for hydrogenation of carbon dioxide. The
catalyst support of the invention comprises a catalyst support
material and an active material capable of catalyzing a reverse
water-gas shift (RWGS) reaction.  In a second aspect, the
present invention relates to a catalyst for use in hydrogenation
of carbon dioxide. The catalyst of the invention comprises a
catalyst for hydrogenation of carbon dioxide supported on a
catalyst support which comprises catalyst support material and an
active material capable of catalyzing a reverse water-gas shift
(RWGS) reaction associated with the catalyst support.
 In a third aspect, the present invention relates to a
method for making a catalyst for use in hydrogenation of carbon
dioxide. In the method, an active material capable of catalyzing a
reverse water-gas shift (RWGS) reaction is applied to a catalyst
support material, then, the combination of the catalyst support
and active material is optionally calcined, and a catalyst for the
hydrogenation of carbon dioxide is deposited on the coated
catalyst support material.
 The invention also relates to a process for hydrogenation
of carbon dioxide, as well as an integrated process for making
syngas comprising a hydrocarbon, esp. methane, reforming step and
a RWGS step which employs the catalyst composition of the present
 The invention further relates to the use of the syngas
mixture obtained with the process according to the invention as
feed material for a process of making a chemical product; such as,
for example, methanol production, olefin and alkane synthesis
(e.g. via Fischer-Tropsch reaction), aromatics production,
oxosynthesis, carbonylation of methanol or carbonylation of
 The invention further relates to a process for making a
chemical product using a syngas mixture as an intermediate or as
feed material, which process comprises a step wherein carbon
dioxide is hydrogenated in the presence of a catalyst according to
the invention. Examples of such a process include methanol
production, olefin and alkane synthesis, aromatics production,
oxosynthesis, carbonylation of methanol or carbonylation of
BRIEF DESCRIPTION OF THE DRAWINGS
 FIG. 1 shows the reactor setup employed in the Examples
for carrying out the hydrogenation of carbon dioxide.
 Figure 2 is an SEM image of a ceria-coated gamma-alumina
support calcined at 800 [deg.]C, with the large ceria-particles
referred to as
, and the alumina support as
The ceria particles have particle sizes ranging from 500-800 nm.
 Figure 3 is an SEM image of the ceria-coated gamma-alumina
support calcined at 500 [deg.]C, with the ceria-particles referred
to as " *", and the alumina support as
The ceria particles have particle sizes ranging from 200-400 nm.
 Figure 4 is an x-ray diffraction pattern of a ceria-coated
gamma-alumina support for FeMnKCeAl calcined at 800 [deg.]C, with
both phases indexed for peak assignment. The sharp and distinct
diffraction peaks, associated with the ceria fluorite phase are a
clear indication of the material's bulk formation. There is only a
small intensity difference between FeMnKCeAl calcined at 500
[deg.]C and FeMnKCeAl calcined at 800 [deg.]C, with the former
showing slightly less sharp peaks.
 Figure 5 shows XPS data, showing wt % of catalysts'
elements. Both FeMnKCeAl calcined at 500 [deg.]C and FeMnKCeAl
calcined at 800 [deg.]C show similar weight distributions, with
FeMnKCeAl calcined at 500 [deg.]C having lower Ce-surface species.
The concentration of surface species is in good agreement with the
results reported over the K/Mn Fe-A1202 catalyst, showing the
comparability of the results.
 Figure 6 shows schematics of the temperature effect on
ceria particle size and the correlated changes in C02 conversion.
With calcination at 500 [deg.]C smaller, more defective particles
are formed leading to the Fe/Mn/K clusters covering larger areas
of the ceria particles. The larger particles formed under
calcination at 800 [deg.]C are covered to a lesser degree by the
Fe Mn/K particles, leading to a higher C02 conversion.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
 For illustrative purposes, the principles of the present
invention are described by referencing various exemplary
embodiments. Although certain embodiments of the invention are
specifically described herein, one of ordinary skill in the art
will readily recognize that the same principles are equally
applicable to, and can be employed in other systems and methods.
Before explaining the disclosed embodiments of the present
invention in detail, it is to be understood that the invention is
not limited in its application to the details of any particular
embodiment shown. Additionally, the terminology used herein is for
the purpose of description and not of limitation. Furthermore,
although certain methods are described with reference to steps
that are presented herein in a certain order, in many instances,
these steps may be performed in any order as may be appreciated by
one skilled in the art; the novel method is therefore not limited
to the particular arrangement of steps disclosed herein.
 It must be noted that as used herein and in the appended
claims, the singular forms "a", "an", and "the" include plural
references unless the context clearly dictates otherwise.
Furthermore, the terms "a" (or "an"), "one or more" and "at least
one" can be used interchangeably herein. The terms "comprising",
"including", "having" and "constructed from" can also be used
 With the catalyst and process according to the present
invention, carbon dioxide can be hydrogenated into carbon monoxide
with high selectivity, the catalyst showing good stability over
time and under variations in processing conditions. Also,
formation of methane is suppressed; typically, only small amounts
of methane are found in the product mixture formed by the process
according to the invention.
 Fischer-Tropsch based reactions are the reactions that
produce hydrocarbons and water from a carbon source, such as
carbon dioxide and carbon monoxide, and hydrogen:
CO+2H2-> -(CH)2- + H20
C02+3H2->-(CH)2- + 2H20
 In a first aspect, the present invention relates to a
catalyst support, which may be used to support various materials
or catalysts for use in reactions for converting carbon dioxide
and hydrogen to hydrocarbons. The catalyst support of the
invention comprises a catalyst support material and another
material associated with the catalyst support material such as a
coating, deposit, impregnation or a material applied by any other
suitable mode of application of a of a material capable of
catalyzing a reverse water-gas shift (RWGS) reaction.
 The catalyst used in the process according to the
invention includes an inert carrier or catalyst support material,
of certain particle size and geometry. Suitable supports include
those materials having good stability at the reaction conditions
to be applied in the process of the invention, and are known by a
person skilled in the art of catalysis. Preferably, the support
material is at least one member selected from the group consisting
of alumina, magnesia, silica, titania, zirconia, sulfated Zr02,
W03Zr02, zeolites such as, for example, H-Beta zeolites, silicas
such as Sylopol(R), A1F3, fluorided A1203, bentonite, and
Si02/Al203, as well as carbon-based supports, molecular sieves
such as mesoporous molecular sieves containing amorphous silica,
e.g. MCM- 41 and MCM-48, and combinations thereof. Gamma-alumina
is a preferred catalyst support material.
 C02 conversion levels reported on catalysts dispersed over
supports made only from these materials have been low since these
supports only act as a stabilizer for the dispersed catalyst.
Lanthanide oxides or (oxy)carbonate, e.g. La203 may also be used
as support, but also contributes to catalyst activity.
 The active material associated with the catalyst support
material is a material which is capable of catalyzing a reverse
water-gas shift reaction (RWGS) reaction. Suitable materials
include, but are not limited to, one or more oxides or carbides of
transition metals or lanthanides. Ceria is the preferred active
material for use in the catalyst support of the present invention.
 Associating the catalyst support with an active material
capable of catalyzing a reverse water-gas shift reaction (RWGS)
reaction provides both a support and an introduced catalytic
activity of the material associated wtih the support, in the form
of reverse water-gas shift catalytic activity. It is known that to
achieve C02 hydrogenation to long-chain hydrocarbons, C02 needs to
initially be converted to CO, which is subsequently converted to
aforementioned hydrocarbons via the Fischer-Tropsch synthesis. The
addition of a material which catalyzes a reverse water-gas shift
reaction (RWGS) reaction facilitates the reverse water-gas shift
reaction (i.e. C02 + H2 <-> CO + H20) and thus leads to an
overall higher C02 conversion relative to a conventional support
containing the same dispersed C02 hydrogenation catalyst.
 Any suitable method may be employed to associate the
active material with the catalyst support material. Suitable
methods include, but are not limited to, an incipient wetness
impregnation method, atomic layer deposition, sol-gel, salt
reduction, precipitation, chemical vapor deposition and
dispersion. As a result, the association between the active
material and the catalyst support material may be as a coating, it
may be impregnated, a deposition layer, the active material may be
bound or attached to the catalyst support material or the active
material be in any other physical form capable of being produced
by the foregoing methods.
 Calcining the catalyst support and active material at
elevated temperatures (i.e. 800 [deg.]C) may lead to the formation
of larger crystallites of the active material, which may be
advantageous relative to smaller crystallites, as the smaller
crystallites appear to be covered to a larger degree by the active
carbon dioxide hydrogenation catalyst which is subsequently
deposited on the catalyst support of the invention. Calcining of
the combined active material and catalyst support of the present
invention at lower temperatures (i.e. 500 [deg.]C) led to an
improvement over an uncoated alumina support in hydrogenation of
carbon dioxide. Calcining can be carried out at any suitable
temperature in the range of 150 to 1300 [deg.]C, preferably in the
range of 450 to 900 [deg.]C and most preferably in the range of
500 to 850 [deg.]C. Calcining is typically carried out over a
period of 10 to 300 minutes, but the duration of calcination can
 Another metal can be added to the active material to
increase the support's reverse water-gas-shift reaction, such as a
transition metal and/or a lanthanide.  The amount of
support material present in the catalyst used in the process
according to the present invention may vary within broad ranges; a
suitable range is from 40 to 95 mass% (based on total mass of
catalyst composition). Preferably, the support forms from 50 to 90
mass%, more preferably from 60 to 85 mass% of total catalyst
composition. In case of lanthanide oxides, the lanthanide content
may vary from 0.1 to 95 mass %.
 The content of the active material may vary within broad
ranges. A certain minimum active material content is needed to
reach a desired level of catalyst activity. A suitable range of
active material is from 1 to 95 mass% (elemental metal based on
total mass of catalyst composition). Preferably, the elemental
metal content is from 5 to 50 mass%, a more preferred range is
from 10 to 20 mass%.
 Forming a stable combination of active material and
catalyst support prior to depositing the C02 hydrogenation
catalyst provides a significantly enhanced C02 conversion in
subsequent conversion reactions conducted over a supported
catalyst fabricated in this manner. Ceria is a preferred active
material for the support since it enhances formation of CO as an
intermediate in the conversion of C02 to hydrocarbons.
Comparatively, the addition of ceria directly to the C02
hydrogenation catalyst, rather than as, for example, a coating on
the catalyst substrate, actually diminishes the C02 conversion
levels of the catalyst material by forming a surface layer over
the catalyst. Thus, the ceria needs to be part of the support in
order to provide the effect demonstrated by the present invention.
 The present invention also relates to a method for making
a catalyst support for use in hydrogenation of carbon dioxide. In
the method, an active material capable of catalyzing a reverse
water-gas shift (RWGS) reaction is associated with a catalyst
support material, the combination of active material and catalyst
support material is optionally calcined, and a catalyst for the
hydrogenation of carbon dioxide is deposited on the calcined
active material and catalyst support material. The method may be
carried out as discussed above, e.g. by application of a coating
to a catalyst support material and optionally calcining the coated
catalyst support material. A suitable catalyst component may
subsequently be deposited on the catalyst support to form a
catalyst for hydrogenation of carbon dioxide.
 The catalyst component that is used in the process of the
invention may be prepared by any conventional catalyst synthesis
method as known in the art. Generally such process includes the
steps of making aqueous solutions of the desired metal components,
for example from their nitrate or other soluble salt;
impregnating the solutions onto a support material; forming a
solid catalyst precursor by precipitation (or impregnation)
followed by removing water and drying; and then calcining the
precursor composition by a thermal treatment in the presence of
oxygen.  The process of the invention shows good catalyst
stability, also at temperatures of above about 600 [deg.]C;
meaning that the composition of the product mixture varies little
over time. The reaction can be performed over a wide pressure
range, from atmospheric conditions up to e.g. 6 MPa.
 Within the context of the present application, a catalyst
that substantially consists of metal oxide, carbide or hydroxide
and other specific elements is understood to mean that the
specified metals in elemental form, or in the form of their
oxides, carbides or hydroxides form the active sites of the
catalyst composition. The catalyst may further comprise other
components, including a support, a binder material, or other
components including usual impurities, as known to the skilled
 In the process according to the invention, any suitable
catalyst for hydrogenation of carbon dioxide may be employed. The
catalyst is immobilized on the coated support of the present
invention. In one embodiment, the catalyst contains one or more
metals in elemental form, or in the form of their oxides, carbides
or hydroxides, wherein the metals are selected from the group
consisting of Fe, K, Mn, Pd, Co, Cr, Ni, La, Ce, W, Pt, Cu, Na, Cs
and various mixtures thereof. One suitable catalyst is a mixture
of iron, manganese and potassium.
 The metal content of the catalyst material may vary within
broad ranges. A certain minimum metal content is needed to reach a
desired level of catalyst activity, but a high content will
increase the chance of particle (active site) agglomeration, and
reduce efficiency of the catalyst. A suitable range is from 1 to
50 mass% (elemental metal based on total mass of catalyst
composition). Preferably, the elemental metal content is from 5 to
30 mass%, a more preferred range is from 10 to 20 mass%.
 The amount of each metal component present in the catalyst
used in the process according to the present invention may vary
within broad limits; a suitable range is from 0.1 to 50 mass %
(metal content based on total mass of catalyst composition).
Preferably, said metal content is from 0.2 to 30 mass %, more
preferably the range is from 0.3 to 20 mass %.
 Preferably, the catalyst used in the process according to
the invention further comprises at least one alkali or alkaline
earth metal, because this further increases surface basicity, and
thus improves the catalyst's yield and selectivity. More
preferably, said alkali or alkaline earth metal is selected from
the group consisting of Li, Na, K, Cs and Sr. The advantage of
such catalysts is that side-reactions in the process of the
invention are effectively suppressed, especially the methanation
reaction. If the catalyst comprises a support material, an
additional advantage of these metals being present is that the
catalyst is more robust, i.e. has better mechanical stability.
 The amount of each alkali or alkaline earth metal
component present in the catalyst used in the process according to
the present invention may vary within broad ranges; a suitable
range is from 0.1 to 50 mass% (metal content based on total mass
of catalyst composition). Preferably, said metal content is from
0.2 to 30 mass%, more preferably the range is from 0.3 to 20
 The catalyst may be applied in the process of the
invention in various geometric forms, for example as spherical
 In the process according to the invention the step of
contacting the gaseous feed mixture containing carbon dioxide and
hydrogen with a catalyst can be performed over a wide temperature
range. As the reaction is endothermic, a high temperature will
promote conversion, but too high temperature may also induce
unwanted reactions; therefore this step is preferably performed at
a temperature ranging from 100 to 500[deg.]C, more preferably from
200 to 450[deg.]C, even more preferred from 250 to 350[deg.]C.
 The step of contacting the gaseous feed mixture containing
carbon dioxide and hydrogen with a catalyst according to the
process of the invention can be performed over a wide pressure
range. A higher pressure tends to enable lower reaction
temperatures, but very high pressures are not practical; therefore
this step is preferably performed at a pressure ranging from 0.1
to 6 MPa, more preferably from 0.5 to 5 MPa, or from 1 to 3.5 MPa.
 The contact time in the step of contacting the gaseous
feed mixture containing carbon dioxide and hydrogen with a
catalyst according to the process of the invention may vary
widely, but is preferable from 0.5 to 6 seconds, more preferably
from 1.5 to 5 seconds, or from 2 to 4 seconds.
 The process according to the invention can be performed in
conventional reactors and apparatuses; which are, for example,
also used in methane reforming reactions. The skilled man will be
able to select a suitable reactor set-up depending on specific
conditions and circumstances. Suitable types of reactors include
continuous fixed bed reactors or a continuous stirred tank
reactor, but are not limited to such reactors. In view of the high
reaction temperature, and catalytic activity of some metals like
Ni in methanation reactions, use of a material comprising Ni or
other active metals for making reactors walls etc. is preferable
avoided. For this reason it is preferred to apply e.g. glass
linings for relevant reactor parts.  In the process
according to the present invention, carbon dioxide is selectively
converted into carbon monoxide by a reverse water gas shift
reaction in the presence of a specific catalyst. The resulting
product of this C02 hydrogenation process is a gas mixture
containing carbon monoxide and water, and non- converted carbon
dioxide and hydrogen. This can, in case of excess hydrogen, also
be represented by the following equation:
 The water formed in this reaction is generally removed
from the product stream, because this will drive the equilibrium
reaction in the desired direction, and because water may interfere
with subsequent reactions of the syngas. Water can be removed from
the product stream using any suitable method known in the art,
e.g. by condensation and liquid/gas separation.
 The amount of hydro gen in the feed gas, that is the value
for n in the above reaction scheme, may vary widely, for example
from n=l to n=5, to result in a syngas composition, e.g. expressed
as its H2/CO ratio or as the stoichiometric number (SN), which can
consequently vary within wide limits. The advantage thereof is
that the syngas composition can be adjusted and controlled to
match the desired use requirements.
 Preferably, SN of the produced syngas mixture is from 0.1
to 4.0; more preferably SN is from 0.5 to 3.5 or even from 1.0 to
3.0. Such syngas product streams can be further employed as feed
stock in different syngas conversion processes, like methanol
formation, olefin synthesis, reduction of iron oxide in steel
production, oxosynthesis, or (hydro)carbonylation reactions.
 The molar ratios of C02 and H2 may be varied in the
reactor to influence the composition of the resulting in a syngas
composition. For example, the feed gas may contain C02 and H2 in
molar ratio of about 1 :3 (n=3 in above equation), resulting in a
syngas composition with H2/CO or SN of about 2; which can be
advantageously used in olefin or methanol synthesis processes.
 The carbon dioxide in the gaseous feed mixture used in the
process of the invention can originate from various sources.
Preferably, the carbon dioxide comes from a waste gas stream, e.g.
from a plant on the same site, like for example from ammonia
synthesis, optionally with (non-catalytic) adjustment of the gas
composition, or after recovering the carbon dioxide from a gas
stream or from the environment. Recycling such carbon dioxide as
starting material in the process of the invention thus contributes
to reducing the amount of carbon dioxide emitted to the atmosphere
(from a chemical production site). The carbon dioxide used as feed
may also at least partly have been removed from the effluent gas
of the RWGS reaction itself.  The gaseous feed mixture
comprising carbon dioxide and hydrogen used in the process of the
invention may further contain other gases, provided that these do
not negatively affect the reaction. Examples of such other gases
include steam or an alkane, like methane, propane or iso-butane.
An advantage of such a process according to the invention is that
the carbon dioxide hydrogenation reaction can be combined and even
integrated with for example steam reforming of methane or with dry
reforming of methane (also called C02 reforming). An additional
advantage hereof is that water formed by C02 hydrogenation can
react with methane to produce more hydrogen; even such that the
water level in the final product is very low.
 The invention thus also relates to an integrated process
for making syngas comprising a hydrocarbon, esp. methane,
reforming step and a RWGS step as defined in the above.
Preferably, the hydrogen to carbon dioxide ratio in the feed
mixture is at least 2 in this combined process according to the
invention, because such excess hydrogen in the gas streams
prevents coke formation, which could otherwise de -activate the
catalyst; and thus this process results in good catalyst
 The invention further relates to the use of the syngas
mixture obtained with the process according to the invention as
feed material for a process of making a chemical product; like
methanol production, olefin and alkane synthesis (e.g. via
Fischer-Tropsch reaction), aromatics production, oxosynthesis,
carbonylation of methanol or carbonylation of olefins.
 The invention therefore further relates to a process for
making a chemical product using a syngas mixture as an
intermediate or as feed material, which process comprises a step
wherein carbon dioxide is hydrogenated according to the invention.
Examples of such a process include methanol production, olefin and
hydrocarbon synthesis, aromatics production, oxosynthesis,
carbonylation of methanol, or carbonylation of olefins.
 The invention will be illustrated by the following
Example 1 Catalyst Support Preparation
 Gamma alumina was used as support material. An incipient
wetness impregnation method was used for catalyst preparation.
Ce(N03)3.6H20 and alumina were added to a flask containing
deionized water at the concentrations required to obtain the
desired weight ratio of 12/100 Ce/Al. These impregnated samples
were then dried at 373K in ambient air. Finally, the support was
calcined at 1073K for 4 hours, under static air conditions.
Subsequently, the active C02 hydrogenation catalyst was dispersed
over the support by co-incipient wetness impregnation (co-IWI).
Description of the support' s operation and use
 The reaction setup wherein the supported catalyst from
Example 1 was employed is shown in Figure 1. C02 hydrogenation
reactions were conducted in a 1 L continuously stirred tank
reactor. In a typical experiment, about 20 g of calcined catalyst
were dispersed in approximately 400 ml of mineral oil (Aldrich)
and subsequently reduced in-situ using CO at 290[deg.]C for 48
hours. Two mass flow controllers regulated by a multi- gas
controller, were used to adjust the flow rate of C02 and H2.
Hydrogenation of C02 was conducted at 290[deg.]C, 200 psig and a
GHSV of 1400 h<"1> at a H2:C02 ratio of 3: 1. The effluent
gases were analyzed online. The pressure in the reactor was kept
 The results showed that use of a Ceria-coated
gamma-alumina as the support for the dispersed C02 hydrogenation
catalyst will increase C02 conversion yield by at least 25% in
comparison to dispersed C02 hydrogenated catalyst over uncoated
gamma-alumina supports. This increase in yield is extremely high
for any process in the petrochemical industry.
 Rather than calcining the catalyst at 800 [deg.]C, the
catalyst, prepared via an identical synthesis route was calcined
at 500 [deg.]C. A 12 wt% Ce/alumina support was prepared using
IWI, which was followed by calcination for 4 hours at 500 [deg.]C.
The temperature at which the treatment occurs plays a pivotal role
in modifying the ceria' s morphology. While ceria nano-particles
calcined at lower temperatures are smaller in diameter and show
more lattice defects/oxygen vacancies, making them more active for
the WGS activity, calcination at a higher temperature results in
larger ceria particles, which concurrently leads to less oxygen
vacancies. Smaller ceria particles have also been reported to be
more easily reduced than larger ones. SEM images of Ce/Al203
particles prepared at the different calcination temperatures show
different particle sizes, with the ceria particles calcined at 500
[deg.]C having particle sizes ranging from 200-400 nm, and the
ceria particles calcined at 800 [deg.]C having particle sizes
ranging from 500-800nm (see Figures 2 and 3). The XRD pattern of
the ceria coated alumina show clear and distinct diffraction peaks
associated with the Ce02 fluorite lattice, corroborating the
presence of large, crystalline particles on top of the alumina
support (see Figure 4).
 Ceria is also known to act as a good growth substrate for
metal clusters. Oxygen vacancies within the ceria lattice result
in the localization of charge over the cations surrounding the
vacancy, which in turn serve as nucleation sites for metal
clusters. Having obtained the modified alumina support, the same
Fe/Mn/K loading, namely 17 wt%, 12 wt% and 8 wt% respectively as
was deposited on the support. However, due to the reduction in
surface area of about 50% (from approximately 200m<2>/g to
100m<2>/g) upon ceria deposition, the amount of
hydrogenation catalyst deposited on the surface was adjusted to
provide the same amount of catalyst per surface area to allow an
appropriate comparison between the samples. Ce02 precipitation
onto alumina is known to significantly reduce the support's
surface area and pore volume, due to plugging of the pores by the
ceria particles. The catalysts prepared had identical K, Mn, Fe
and Ce loadings, with the only variation between them being the
different calcination temperature of the Ce-impregnated support
(denoted FeMnKCeA1500 and FeMnKCeA1800 for supports calcined at
500 [deg.]C and 800 [deg.]C, respectively).
 Both the FeMnKCeA1500 and FeMnKCeA1800 were tested for
their activity in C02 hydrogenation, to establish the effect the
calcination temperature has on C02 conversion ability. Based on
the increased WGS activity of smaller ceria particles, one may
expect that the FeMnKCeA1500 would outperform the
FeMnKCeA1800 catalyst, showing that smaller nanoparticles
containing more defects perform better in the RWGS reaction. Both
catalysts showed a marked improvement in C02 conversion in
comparison to the ceria- free catalyst, with C02 conversion
increasing from 41.4% to 47.5% over the FeMnKCeA1500 catalyst and
C02 conversion of 50.4% over the FeMnKCeA1800. Furthermore,
besides the increase in C02 conversion a reduction in methane
formation was observed over both the FeMnKCeA1500 catalyst and the
FeMnKCeA1800 catalyst, in comparison to the ceria-free catalyst.
Both catalysts also showed an increase in CO production relative
to the ceria-free catalyst. All catalyst show comparable
olefin/paraffin ratios as well as an equivalent affinity for the
formation of the C2-C5+ fraction as shown in Table 1 below.
 The lower C02 conversion over the FeMnKCeA1500 catalyst in
comparison to the FeMnKCeA1800 catalyst can be explained on the
basis that coverage of the active sites for chain growth by other
co-catalysts per unit surface area available has resulted in a
diminished activity. FeMnKCeA1500 has a lower concentration of
ceria surface species in comparison to FeMnKCeA1800 (by approx.
42%) as was deduced from XPS analyses (see Figure 5). It can be
concluded that upon precipitation of Fe, Mn and K onto the treated
support, these metals form on top of the ceria grains resulting in
a reduced availability of the active ceria sites for the RWGS.
 The reduced C02 conversion of FeMnKCe500 in comparison to
FeMnKCe800 can be explained by the better dispersion of the C02
hydrogenation catalyst over the smaller ceria particles. As the
number of defect sites on the ceria surface increases and thus the
number of sites for Fe/Mn/K particle crystallization also
increases, the C02 hydrogenation catalyst will be better dispersed
over the ceria calcined at the lower temperature, resulting in a
reduced surface availability of the ceria for the RWGS reaction to
occur (see Figure 6 for a schematic diagram of the catalytic
system). Even though surface ceria is reduced by approximately 42%
in FeMnKCeA1500 compared to FeMnKCeA1800 (see Table 2), the
activity is only diminished by about 32%. This is indicative of
the smaller ceria particles being indeed more active for the RWGS,
showing an elevated reducibility and thus leading to a higher
concentration of active sites per surface area for the RWGS.
 These examples have shown a significant improvement of C02
hydrogenation ability over the iron- based catalyst through the
addition of ceria. A truly bifunctional catalyst has been created
that converts C02/H2 to valuable HC by carefully adjusting the
synthesis procedures. The present catalyst incorporates both RWGS
activity and chain-growth to yield high C02 conversion levels. The
addition of ceria prior to the deposition of the C02 hydrogenation
catalyst results in an approximately 22% increase in C02
conversion, while the product selectivity is not detrimentally
affected. It has also been shown that the calcination temperature
prior to the deposition of Fe/Mn/K and the correlated ceria
particle size may be used to tailor the catalyst' s activity.
Experimental Methods used in the Examples
 20g of calcined catalyst were dispersed in approximately
400 ml of mineral oil (Aldrich) in a 1L three-phase slurry
continuously stirred tank reactor (CSTR). Testing apparatus and
conditions are reported in Dorner, R. W., Hardy, D. R., Williams,
F. W., and Willauer, H. D., Applied Catalysis A: General (2009)..
Time- on-stream (TOS) for the catalyst was 100 hours.
 BET surface areas were measured using a Micromeritics
ASAP2010 accelerated surface area and porosimetry system. An
appropriate amount (-0.25 g) of catalyst sample was taken and
slowly heated to 200 [deg.]C for 10 h under vacuum (~50 m Torr).
The sample was then transferred to the adsorption unit, and the N2
adsorption was measured at the boiling temperature of nitrogen (T
= -196 [deg.]C).
 Powder x-ray diffraction (XRD) measurements were performed
on all spent catalyst materials. The catalyst was washed in
heptane before XRD measurements were taken to remove the mineral
oil from the solids. The catalyst was subsequently recovered by
conventional filtering procedures. The data were collected on a D8
Siemens Bruker diffractometer with a general area detector
employing the Bragg-Brentano geometry and the CuKal wavelength.
The data were collected in the 20-50[deg.] 2[Theta] range with a
step increment of 0.01[deg.] and the time for each step was 2
 XPS measurements were performed on all spent catalyst
materials and were used to assess the surface species and
quantities present on the powder particles. The XPS studies were
carried out using a K- Alpha machine (Thermo Scientific, UK) and
the Unifit software (Hesse, R., Chasse, T., and Szargan, R.,
Analytical and Bioanalytical Chemistry 375 (7), 856 (2003)) for
data analysis, using the instrument specific powder sample holder.
The system's base pressure was less than 5 x 10<~9> mbar,
however the pressure in the analysis chamber during data
collection and analysis was 2 x 10<~7> mbar due to the use
of the low-energy electron flood gun for charge neutralization. A
monochromated Al Ka (hv = 1486.6 eV) was used as the x-ray source.
The instrument is regularly calibrated to the binding energies
(BE) of Au, Cu and Ag peaks. The C Is, O Is and Al 2p BE are used
as internal standards. The Al/C signal ratio (3/2) is almost
constant for all samples, ensuring comparability of collected
data. All atomic percentages obtained by XPS in this work are
converted to weight percentages for comparability sake. 
Structural and chemical characterization was performed with a
field emission scanning electron microscope (FESEM) - Model LEO
DSM 982, LEO. The SEM was operated at an accelerating voltage of 5
kV and the working distance varied from 3 to 8mm. The powder was
placed under the SEM detector as a loosely scattered powder stuck
to conducting tape. All particle sizes quoted in this paper are
average particle sizes representative of the total sample.
 It is to be understood that even though numerous
characteristics and advantages of the present invention have been
set forth in the foregoing description, together with details of
the structure and function of the invention, the disclosure is
illustrative only, and changes may be made in detail, especially
in matters of shape, size and arrangement of parts within the
principles of the invention to the full extent indicated by the
broad general meaning of the terms in which the appended claims
Direct reacting anolyte-catholyte fuel cell for hybrid
A fuel cell and a method for using the fuel cell to make
electricity, in which the fuel cell has an anode half-cell having
an electrocatalytic anode and a liquid anolyte that is
substantially isopropanol dissolved in seawater. The fuel cell has
a cathode half-cell having an electrocatalytic cathode and a
liquid catholyte that is substantially hydrogen peroxide dissolved
in slightly acidic seawater. The half-cells share a common proton
exchange membrane. When the anode and cathode are in electrical
connection the isopropanol is oxidized to carbon dioxide, which is
fugitive, and the hydrogen peroxide is reduced to water. In the
method, the anolyte and the catholyte, which are in effect the
fuel of the fuel cell, are metered and re-circulated as needed to
produce the necessary electrical power. The electrocatalytic
electrodes are typically comprised of palladium and iridium
METHOD FOR ACCELERATING DECOMPOSITION OF
PROBLEM TO BE SOLVED: To provide a method for quickly, safely and
certainly accelerating decomposition of hydrogen peroxide to a
natural level by a simple operation, the hydrogen peroxide being
contained in water, especially in seawater, brackish water, fresh
water or industrial water to which the hydrogen peroxide is added
for various treatments and in which the hydrogen peroxide remains
after the treatments. ; SOLUTION: The method for accelerating
decomposition of hydrogen peroxide is characterized in that the
water containing the hydrogen peroxide is brought into contact
with a metal structure on which a palladium nitrate powder is
thermally sprayed and at the same time a dc voltage is applied
between an anode and a cathode arranged in an optional position in
contact with the water containing the hydrogen peroxide.
Civil liquid fuel and preparation method
The invention relates to a civil liquid fuel and a preparation
method thereof. The civil liquid fuel is prepared from the
following raw materials by weight percent: 10%-35% of seawater or
treated wastewater, 65%-90% of methanol, 0.2%-1% of xylene,
0.05%-0.1% of cyclohexane, 0.05%-0.5% of butyl acetate, 0.2%-1% of
ammonium nitrate, 0.2%-1% of hydrogen peroxide with the mass
concentration of 27% and 0.3%-1.5% of ethanol. The civil liquid
fuel has simple preparation method, accessible raw materials,
stable performance and safe transportation and use, have high heat
value and can be completely burnt, do not generate pressure and do
not explode; and the civil liquid fuel can be extinguished with
water and be characterized by cleanliness, less emissions of
production, environmental protection, safety and low cost.; The
invention can replace diesel and liquefied natural gas (LNG) and
be suitable to be used in the diesel oil furnaces, boilers,
liquefied gas furnaces and the like of various hotels, schools,
factories, institutions and the like.
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