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EPAoverreach-2014b

US Navy Improves CO2 Hydrogenation Catalyst

United States Patent Application: 0110105630

We have now many times documented the plain fact, that, our own United States Government, through the United States Navy and the United States Department of Defense, now has in hand the technologies which would, if implemented, allow us to begin harvesting Carbon Dioxide from any available source, including the environment itself, and, then, to start converting that reclaimed Carbon Dioxide into liquid hydrocarbon fuels.

Some examples of our reportage on that issue can be accessed via:

US Navy Awarded September, 2011, CO2 Recycling Patent | Research & Development; concerning: "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2; September 13, 2011; Inventors:Nick Tran, Dennis Hardy, et. al., DC and VA; Assignee: The United States of America as represented by the Secretary of the Navy; Abstract: A method of: introducing hydrogen and a feed gas containing at least 50 % carbon dioxide into a reactor containing a Fischer-Tropsch catalyst; and heating the hydrogen and carbon dioxide to a temperature of at least about 190 C. to produce hydrocarbons in the reactor. An apparatus having: a reaction vessel for containing a Fischer-Tropsch catalyst, capable of heating gases to at least about 190 C.; a hydrogen delivery system feeding into the reaction vessel; a carbon dioxide delivery system for delivering a feed gas containing at least 50 % carbon dioxide feeding into the reaction vessel; and a trap for collecting hydrocarbons generated in the reaction vessel"; and:

US Navy and Columbia University Recycle Atmospheric CO2 | Research & Development; which includes information concerning:  "United States Patent 7,420,004 - Process and System for Producing Synthetic Liquid Hydrocarbon Fuels; September, 2008; Inventors: Dennis Hardy and Timothy Coffey, VA; Assignee: The USA as Represented by the Secretary of the Navy; Abstract: A process for producing synthetic hydrocarbons that reacts carbon dioxide, obtained from seawater or air, and hydrogen obtained from water, with a catalyst in a chemical process such as reverse water gas shift combined with Fischer Tropsch synthesis".

Herein, we further demonstrate just how thorough and how complete our US Navy's science and technology for converting Carbon Dioxide, "obtained from seawater or air", or, we would suppose, any other handy source, into liquid hydrocarbon fuels actually is.

They have improved the structure and composition of the catalyst and catalyst support which can be utilized in the above processes of "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2" and "United States Patent 7,420,004 - Process and System for Producing Synthetic Liquid Hydrocarbon Fuels", to convert Carbon Dioxide, reclaimed from whatever source, into conventional forms of liquid hydrocarbons.

As seen, with comment appended, in excerpts from the initial link in this dispatch to:

"US Patent Application 20110105630 - Catalytic Support for use in Carbon Dioxide Hydrogenation

Date: May, 2011

Inventors: Robert Dorner, et. al., IL, VA and MD

Assignee: The Government of the USA as represented by the Secretary of the Navy, DC

Abstract: 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.

(Concerning the above "reverse water-gas shift", i.e., CO2 + H2 = CO + H2O, see: RWGS.)

Claims: A catalyst support suitable for use in supporting a catalyst for hydrogenating carbon dioxide, the catalyst support comprising a catalyst support material and an active material capable of catalyzing a reverse water-gas shift reaction associated with the catalyst support material. 

A catalyst support ...  wherein the catalyst support material is selected from the group consisting of alumina, magnesia, silica, titania, zirconia (and others).

A catalyst support ... wherein the active material is selected from the group consisting of one or more oxides of Lanthanum, Cerium, (and others specified). 

A catalyst support ... wherein the catalyst support material comprises alumina and the active material comprises ceria. 

A catalyst comprising the catalyst support ... and a catalyst material immobilized on the catalyst support. 

A catalyst ... wherein the catalyst material comprises one more metals in elemental form or in the form of oxides, hydroxides or carbides, said metals being selected from the group consisting of Iron, Potassium, Manganese (and others specified) and various mixtures thereof. 

A method for making a catalyst support comprising the step of: associating an active material capable of catalyzing a reverse water-gas shift reaction with a catalyst support material. 

A method as claimed ... further comprising the step of calcining the associated active material and the catalyst support material ... at a temperature of from about 300 to about 1300C. 

A method ... wherein the catalyst support material is selected from the group consisting of alumina, magnesia, silica, titania, zirconia, ... zeolites, and (others). 

A method ... wherein the active material comprises ceria. 

A method for hydrogenation of carbon dioxide comprising the step of reacting hydrogen and carbon dioxide in the presence of a catalyst comprising a catalyst support material, an active material capable of catalyzing a reverse water-gas shift reaction associated with the catalyst support material and a catalyst material suitable for catalysis of a hydrogenation reaction located on the coated catalyst support material (all as further specified).

Background and Field: Thermochemical CO2 conversion ... 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.

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 CO2 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 CO2 dissolved in the ocean (primarily in the form of bicarbonate) and hydrogen through the electrolysis of water.

CO2 and H2 can subsequently be reacted over a heterogeneous catalyst to form hydrocarbons of desired chain length and type.

The target of achieving a high yield, high selectivity process for CO2 hydrogenation to jet fuel can be achieved by use of a two step synthesis process, involving initial CO2/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 ... 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 CO2 hydrogenation has not been observed before.

Consequently, a two-step process is advantageous in comparison to the direct route to jet-fuel.

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.

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 invention. 

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, (etc.).

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 ... .

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 ... 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."

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First, any CO2 in "the effluent gas of the RWGS reaction" is just CO2 that wasn't reacted with Hydrogen and converted into Carbon Monoxide. There is an equilibrium in the RWGS, which we don't pretend to understand, that prevents 100% of the initial Carbon Dioxide from being reacted. So, the CO2 in "the effluent gas of the RWGS reaction" is likely to be CO2 that was added from outside the system as a raw material in the first place, and just passed through. The RWGS of this invention is not, as we understand it, generating additional Carbon Dioxide.

What we do need to make this whole thing work is added elemental Hydrogen, which, as we've documented in several reports, including:

More NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,051,005 - Photolytic Production of Hydrogen; 1977; Assignee: United Technologies Corporation;

Government Interests: The invention described herein was made in the course of a contract with the National Aeronautics and Space Administration. Abstract: Hydrogen and oxygen are produced from water in a process involving the photo-dissociation of molecular bromine with radiant energy at wavelengths within the visible light region"; and:

General Electric Hydrogen from Geothermal Energy | Research & Development; concerning: "United States Patent 7,331,179 - System and Method for Production of Hydrogen; 2008; Assignee: General Electric Company; Abstract: A technique is disclosed for a system and method for combined production of power and hydrogen utilizing the heat from a first working fluid heated by a geothermal energy source using a steam generator and an electrolyzer designed to receive the steam produced by the steam generator for the production of hydrogen and oxygen using electrolysis"; and:

West Virginia Coal Association | Germany & Pennsylvania Hydrogen from Hydropower | Research & Development; concerning: "United States Patent 6,864,596 - Hydrogen Production from Hydro Power; 2005; Assignees: Voith Siemens Hydropower Generation GmbH and Incorporated, Germany and York, PA";

we do have some sustainable ways of making a little of.

And, the point, the question, maybe, is:

Would we rather spend money to make Hydrogen, for use in the United States Navy's process of our subject herein, "US Patent Application 20110105630 - Catalytic Support for use in Carbon Dioxide Hydrogenation", so that we can start making such interesting things as "methanol", and various hydrocarbon fuels, out of "carbon dioxide ... from a waste gas stream"; or, would we rather, through Cap & Trade taxation, punish the generators of that "waste gas stream", and the customers for the electricity that was generated along with the "carbon dioxide"; or, would we rather, through mandated Geologic Sequestration, economically enslave those users of Coal-based electricity into the service of Big Oil and his secondary petroleum scrounging in nearly-depleted natural oil reservoirs; or, would we rather continuing our entire nation's military and economic enslavement to the less-than savory foreign powers of OPEC?

That's a lengthy, and inelegantly composed, question.

But, in its essence, it's a simple one.

And, the answer, we think, should be simple, too.

If someone says that it isn't so simple, then, we contend, it's the motives of the doubters that might, in fact, be what's complicated, more complicated than we, the public citizens of US Coal Country, might want to be the case.

And, maybe we should start to have some doubts, and start to ask some questions, of our own.