United States Patent: 8658554

One might be tempted to call it treason.

Genuine patriots in the employ of our United States Government, as that Government is impeccably embodied in the United States Navy, have laid the foundations for the United States of America to become completely self-sufficient in her supply of liquid hydrocarbon fuels and, thus, to end, to sever forever, her crippling, debasing, enslaving and junkie-like dependence on OPEC oil.

 

But:

Those in positions to educate and inform all United States citizens of that miraculous delivery from disabling economic servitude remain silent, or they content themselves by persistently trying to fan interest in what are, really, nothing more than the flashy carnival side shows of American energy production: garish and ultimately transient farces, the benefits of which have been vastly overstated, and which we won't grace here by naming.

That silence persists, while, as seen for three examples in:

US Navy 2008 CO2 to Synfuel | Research & Development | News; concerning: "United States Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels; 2008; Inventors: Dennis Hardy and Timothy Coffey; 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. The hydrogen is produced by ... (a) source that is fossil fuel-free, such as wind or wave energy. The process can be either land based or sea based. A system for producing synthetic hydrocarbons, comprising: (a) a unit for recovering carbon dioxide from seawater, air, or a combination thereof; (b) a unit for producing hydrogen from water; and (c) a Fischer Tropsch synthesis unit wherein ... methanol production is combined with Fischer Tropsch synthesis to produce said hydrocarbons from said carbon dioxide and said hydrogen"; and:

The US Navy Recycles CO2 into Liquid Hydrocarbo?n Fuels | Research & Development | News; concerning: "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2; 2011; Inventors: Nick Tran, Dennis Hardy, et. al.; 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 ....; 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 May 7, 2013, CO2 to Liquid Hydrocarbon Fuels | Research & Development | News; concerning: "United States Patent 8,436,457 - Synthesis of Hydrocarbons Via Catalytic Reduction of CO2; 2013; Inventors: Nick Tran, Dennis Hardy, Samuel Lambrakos, John Michopoulos; 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 vol % carbon dioxide into a reactor containing a Fischer-Tropsch catalyst; and heating the hydrogen and carbon dioxide ... to produce hydrocarbons in the reactor. An apparatus comprising: a reaction vessel containing a kieselguhr supported catalyst comprising cobalt, potassium, thorium, and magnesium, capable of heating gases contained therein to at least about 190 C; a hydrogen delivery system feeding into the reaction vessel; a carbon dioxide delivery system feeding into the reaction vessel that delivers a feed gas containing at least 50 vol % carbon dioxide; and a trap that collects hydrocarbons generated in the reaction vessel; wherein the hydrogen delivery system extracts hydrogen from water or the carbon dioxide delivery system extracts carbon dioxide from seawater";

our United States Navy, totally unheralded, has been steaming full ahead, developing all the technology we need to, as in "US Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels", harness environmental, "wind or wave", energy, and, then, to use that essentially-infinite and carbon-free energy to synthesize fuel alcohol "methanol" and "liquid hydrocarbons" from nothing but plentiful and constantly-renewing "seawater" and Carbon Dioxide.

Another US Navy technology for synthesizing hydrocarbon fuels from water and Carbon Dioxide was disclosed in our report a shade more than two years ago of:

US Navy Improves CO2 Hydrogenation Catalyst | Research & Development | News; concerning: "United States Patent Application 20110105630 - Catalytic Support for use in Carbon Dioxide Hydrogenation; 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) ... Claims: A catalyst support suitable for use in supporting a catalyst for hydrogenating carbon dioxide ... . 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. 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. ... 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 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 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)".

And, herein, we learn that the above "United States Patent Application 20110105630 - Catalytic Support for use in Carbon Dioxide Hydrogenation", was just recently confirmed as valid and practicable technology by technical experts in the employ of our United States Government's Patent and Trademark Office, through their issuance of:

"United State Patent 8,658,554 - Catalytic Support for Use In Carbon Dioxide Hydrogenation Reactions

Catalytic support for use in carbon dioxide hydrogenation reactions - The United States of America, as represented by the Secr

Date: February 25, 2014

Inventors: Robert Dorner, Heather Willauer, and Dennis Hardy, IL, VA and MD

Assignee: The United States of America as Represented by the Secretary of the Navy

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.

(Though not well explained, synthetic natural gas Methane is one of the products of the initial CO2 hydrogenation, and, which Methane is later specified to be further reformed into more hydrocarbon "syngas", which syngas is then added to the bulk of the syngas generated from CO2, with all of it then catalytically condensed into hydrocarbons. However, we must point out that the opportunity might exist here to generate substitute natural gas Methane as the byproduct of a process focused primarily on the synthesis of liquid hydrocarbons from Carbon Dioxide.)

Claims: A catalyst support supporting a catalyst for hydrogenating carbon dioxide and thereby forming long chain hydrocarbons, the catalyst support comprising a catalyst support material capable of forming long chain hydrocarbons and an active material capable of catalyzing a reverse water-gas shift reaction associated with the catalyst support material; wherein the catalyst support material comprises ceria; and wherein the active material comprises iron carbide. 

A catalyst comprising the catalyst support of claim 1 and a catalyst material immobilized on the catalyst support (and, a) catalyst as claimed in claim 2, 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 K, Mn, Pd, Co, Cr, Ni, La, Ce, W, Pt, Cu, Na, Cs and various mixtures thereof.

A method for making a catalyst support for use in carbon dioxide hydrogenation reactions and the formation of long chain hydrocarbons comprising the step of: associating an active material capable of catalyzing a reverse water-gas shift reaction with a catalyst support material capable of forming long chain hydrocarbons; wherein the catalyst support material comprises ceria; and wherein the active material comprises iron carbide.

Background and 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.

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.

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, oxosynthesis, carbonylation of methanol or carbonylation of olefins. 

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 olefins."

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Again: "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".

We haven't reproduced many of the technical details, letting it suffice for now that experts in our United States Government know and understand them. But, concerning the above "harvesting CO2 dissolved in the ocean (primarily in the form of bicarbonate", so that such harvested CO2 can then be converted into hydrocarbons, via the process disclosed by "United State Patent 8,658,554 - Catalytic Support for Use In Carbon Dioxide Hydrogenation Reactions", one of the named inventors of USP 8,658,554, "Heather Willauer", as seen in our report of:

US Navy Recovers Environmental CO2 for Hydrocarbon Synthesis | Research & Development | News; concerning: "United States Patent 8,313,557 - Recovery of CO2 from Seawater/Aqueous Bicarbonate Systems; Date: November 20, 2012; Inventors: Heather Willauer, et. al., VA and MD; Assignee: The United States of America as Represented by the Secretary of the Navy; Abstract: 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. The ocean is a possible resource for carbon dioxide. In the atmosphere, the concentration of CO2 approximately is 370 ppm (and) CO2 in seawater is about 140 times greater than air. (If) carbon dioxide could be economically and efficiently extracted ... (then it) could be proposed to utilize this carbon as a chemical feedstock in processes such as catalytic polymerization with hydrogen";

has been taking the lead, with a team of her colleagues, in an effort focused on developing the means for efficiently extracting, harvesting, Carbon Dioxide from our richest environmental store of it, the oceans, so that CO2 can be used "as a chemical feedstock in processes" like, we presume, the above "United State Patent 8,658,554 - Catalytic Support for Use In Carbon Dioxide Hydrogenation Reactions". 

And, as we can learn following, the Navy team led by the accomplished Heather Willauer has continued to develop and refine the processes whereby we can efficiently extract Carbon Dioxide from seawater, and, again, thereby making it available as a raw material for the synthesis of hydrocarbons.

Comment follows excerpts from the links to the quite recent:

United States Patent: 8663365 - Method for the Continuous Recovery of Carbon Dioxide from Acidified Seawater

Method for the continuous recovery of carbon dioxide from acidified seawater - The United States of America, as represented by

Date: March 4, 2014

Inventors: Heather Willauer, et. al., VA, WV, CT, VA and MD

Assignee: The United States of America as represented by the Secretary of the Navy

Abstract: 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 CO2 is removed from the natural seawater.

Description: An electrochemical method to acidify seawater and recover CO2 simultaneously with hydrogen gas from alkaline water sources such as seawater has been developed at the Naval Research Laboratory. (U.S. patent application Ser. No. 12/958,963 filed on Nov. 17, 2011 by Felice DiMascio, the entire contents of which are incorporated herein by reference.) ... To complement this technology, the Naval Research Laboratory has developed the present invention to enhance re-equilibrated CO2 recovery up to 92% from seawater at pH of  less than or equal to 4.

(Concerning the above-cited DiMascio CO2 recovery invention, see our report of:

US Navy Harvests CO2 from Seawater for Hydrocarbon Synthesis | Research & Development | News; concerning: "United States Patent Application 20130206605 - Extraction of Carbon Dioxide and Hydrogen from Seawater and Hydrocarbon Production Therefrom; 2013; Inventors: Felice DiMascio, Dennis Hardy, et. al., CT, MD, VA and PA; Assignee: The Government of the United States of America as represented by the Secretary of the Navy; Abstract: 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 produce hydrocarbons".)

Summary: The present invention provides a method for recovering re-equilibrated CO2 from acidified natural seawater using a membrane contactor and passing seawater with a pH .ltoreq.6 over the outside of the hollow fiber membrane tube while applying vacuum or a hydrogen sweep gas to the inside of the membrane tube, wherein up to 92% of the re-equilibrated CO2 is removed from the natural seawater.

A method for the recovery of re-equilibrated CO2 from acidified natural seawater, comprising: passing seawater with a pH less than or equal to 6 over the outside of a hollow fiber membrane tube in a membrane contactor; and simultaneously using hydrogen as a sweep gas on the inside of the hollow fiber membrane tube at a flow rate of 360 mL/min or higher; wherein 69 to 92% of the carbon dioxide is removed from the natural seawater".

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Should the point not be clear to you:

The United States Navy says, as confirmed by technical experts in a separate branch of our United States Government, that:

We can efficiently collect Carbon Dioxide from our environment, from "natural seawater", and, then, as a practical matter, using freely-available environmental energy, such as "wind or wave energy", to drive the process, we can convert that Carbon Dioxide, along with Hydrogen concurrently extracted from non-potable "seawater", into - - along with, if we want it, some substitute natural gas "methane" - - fuel alcohol "methanol" and "long-chain hydrocarbons" such as "jet fuel".

The "methanol", we remind you, can be directly converted into Gasoline via ExxonMobil's "MTG"(r), methanol-to-gasoline, process. 

We, here, know now it won't be, but, this is news that Coal Country patriots should be shouting in the streets while they wave flags in the air; it should be headlined in Coal Country newspapers.

According to the United States Government itself, as herein, we can put an end to our imports of foreign petroleum and the concurrent, uncontrolled hemorrhaging of our national wealth; we can put an end to the Cap and Trade tax threats to our economically essential generation of truly abundant, truly reliable and truly affordable electricity from our vast reserves of domestic US Coal; we can put a lot more United States citizens to work; and, we can stop fighting wars in the Middle East and Arabia. 

There is no - - there can no longer be any - - doubt: 

In processes driven by environmental energy, we can collect Carbon Dioxide from the environment, or from our varied industrial processes, and, then, we can convert that CO2, along with non-potable water, into anything and everything we now import from OPEC.

And, it is time, maybe far past time, that plain truth was told.

"There comes a time when silence is betrayal." - Martin Luther King, Jr.


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