United States Patent Application: 0140131192

We were actually researching some improved methods for the conversion of Coal and Carbon-recycling botanical matter and wastes into synthetic petroleum today, when our US Government elected to publish the subject of this hastily-composed dispatch, i.e.: yet another formal description of technology developed, by Arizona State University, in an effort paid for with the taxes collected by our US Government from all of us, whereby freely-available environmental energy can be harnessed to power the conversion of Carbon Dioxide, as harvested from whatever handy source, into substitute natural gas Methane.

 

And there is a punch line that shouldn't be ignored, by anyone. We'll get to that.

First, we remind you, that, as seen for only one now out of many, many examples, in our report of:

Panasonic Solar Energy Converts More CO2 into Methane | Research & Development | News; concerning: "United States Patent 8,617,375 - Method for Reducing Carbon Dioxide; December 31, 2013; Assignee: Panasonic Corporation, Osaka (Japan);  Abstract: The method for reducing carbon dioxide of the present invention includes a step (a) and a step (b) as follows. A step (a) of preparing an electrochemical cell. The electrochemical cell comprises a working electrode, a counter electrode and a vessel. The vessel stores an electrolytic solution. The working electrode contains boron carbide. The electrolytic solution contains carbon dioxide. The working electrode and the counter electrode are in contact with the electrolytic solution. A step (b) of applying a negative voltage and a positive voltage to the working electrode and the counter electrode, respectively, to reduce the carbon dioxide. ... In the electrolytic reduction method, the reducing reaction proceeds even at an ordinary temperature and ordinary pressure. The electrolytic reduction method requires no large-scale equipment. Thus, the electrolytic reduction method is simpler than the catalytic hydrogenation method. Accordingly, the electrolytic reduction method is considered as an effective CO2 reduction method.(It) is an object of the present invention to provide a method for reducing carbon dioxide using a highly-durable catalyst that is capable of reducing CO2 at an overvoltage equal to or lower than overvoltages required for conventional catalysts to produce highly useful substances (such as) formic acid (HCOOH), methane (CH4), ethylene (C2H4), and ethane (C2H6)). (Boron Carbide) used as a catalyst in reducing CO2 causes the reducing reaction of CO2 only with an external energy from DC power supply at ordinary temperature. Moreover, the method for reducing CO2 of the present invention can be applied to methods using a solar cell as an external power supply. The catalyst for reducing CO2 can be applied, by combination with a photocatalyst, to catalysts that can be used with solar energy";

technologies are proliferating around the world, whereby solar light energy can be used to drive the conversion of Carbon Dioxide into, among other valuable hydrocarbon compounds, substitute natural gas "methane (CH4)".

The above Panasonic Corporation has been at work developing such artificial photosynthesis, Carbon Dioxide-to-Hydrocarbons technology for quite some time now. And, the precedent versions of their, and other companies', technologies of artificial photosynthesis, about some of which we have reported, were said by some to "suffer" from inefficiency - - that, even though our study here of those technologies, and, of natural photosynthesis, led us to draw the conclusion that the artificial photosynthesis technologies were actually several times more efficient than natural photosynthesis, in general terms of energy consumed versus Carbon Dioxide utilized.

We're uncertain of the efficiencies of Panasonic's above "United States Patent 8,617,375 - Method for Reducing Carbon Dioxide", but, note that a range of products is made from Carbon Dioxide in that process, as is the case in most artificial photosynthesis technologies.

Our "punch line" herein, as we noted above, is this:

The artificial photosynthesis CO2-to-Methane technology and highly-active catalyst developed herein, with United States Government funding, by Arizona State University is actually specific to the synthesis of substitute natural gas Methane. Few other products, like Carbon Monoxide, are generated, and, those that are generated appear only in relatively small amounts.

And, we think even more importantly, documented experiments, recorded herein, with Arizona State University's innovative CO2-to-Methane artificial photosynthesis catalyst demonstrate, as ASU puts it:

"the real-world application of this material in CO2 photoreduction. The CH4 (Methane) production rate (observed and specified) is about 20-30 times higher as compared to the highest CH4 production rate using other modified TiO2 structure reported in the literature".

Much of that will be highlighted in excerpts from our subject today:

"United States Patent Application 20140131192 - Ionic Liquid Functionalized Reduced Graphite Oxide / TiO2 Nanocomposite for Conversion of CO2 to CH4

Ionic Liquid Functionalized Reduced Graphite Oxide / TiO2 Nanocomposite for Conversion of CO2 to CH4 - Andino, Jean

Date: May 15, 2014

Inventors: Jean Andino and Tingling Gao, Arizona

(As we've many times noted, early version of US Patent Applications don't often publish the name of the ultimate Assignee of Rights to the invention, if and when a United States Patent issues. However, as can be learned via:

EAGER: Reduction of Carbon Dioxide to Methane / Global Institute of Sustainability / Arizona State University; which concerns the Arizona State University's Global Institute of Sustainability, and their work on the "Reduction of Carbon Dioxide to Methane", Dr. Jean Andino is a professor at Arizona State University.

And, as can be learned via:

Student’s work will help in fight against air pollution | ASU Engineering; as of July, 2010, co-inventor Tingling Gao was a student working on her PhD, in the field of Environmental Engineering, at Arizona State University, with Professor Jean Andino serving as her faculty advisor.)

Abstract: An ionic liquid functionalized reduced graphite oxide (IL-RGO)/TiO2 (titanium oxide) nanocomposite was synthesized and used to reduce CO2 to a hydrocarbon in the presence of H2O vapor. 

Government Interests: The invention was made with government support under 1253443 awarded by the National Science Foundation. The United States government has certain rights in the invention.

Claims: A photocatalytic nanocomposite comprising: a reduced graphite oxide; a photocatalytic metal oxide in nanoparticle form; wherein the photocatalytic metal oxide in nanoparticle form is dispersed in the reduced graphite oxide. 

The photocatalytic nanocomposite ... further comprising an ionic (component) attached to the reduced graphite oxide (and) wherein the ionic (component) comprises (compounds as described and specified, and).

wherein the reduced graphite oxide is an ionic liquid functionalized reduced graphite oxide formed by attaching a NH2-terminated ionic liquid to the reduced graphite oxide.

The photocatalytic nanocomposite ... wherein the photocatalytic metal oxide is TiO2 (and) wherein the TiO2 is in the form of rutile and anatase (and) wherein the reduced graphite oxide is a powder. 

A method of making a photocatalytic nanocomposite comprising: oxidizing graphite to form a reduced graphite oxide; mixing the reduced graphite oxide with TiO2 nanoparticles to form the photocatalytic nanocomposite (and as further described).

(The "TiO2", Titanium Dioxide, or, variously, Titanate, and compounds of it in combination with some other elements, have long been known to exhibit photocatalytic activity, especially with regards to Carbon Dioxide photochemical processes. And, as seen for another example in our report of:

USDOE Hires Nevada to Photo-Convert CO2 into Fuels | Research & Development | News; concerning: "United States Patent 8,709,304 - Hydrothermal Synthesis of Nanocubes of Sillenite Type Compounds for Photovoltaic Applications and Solar Energy Conversion of Carbon Dioxide to Fuels; April 29, 2014; Inventors: Vaidyanathan Subramanian and Sankaran Murugesan, NV and TX; Assignee: Board of Regents of the Nevada System of Higher Education, on behalf of the University of Nevada; Abstract: The present invention relates to formation of nanocubes of sillenite type compounds, such as bismuth titanate, i.e., Bi12TiO20, nanocubes, via a hydrothermal synthesis process, with the resulting compound(s) having multifunctional properties such as being useful in solar energy conversion, environmental remediation, and/or energy storage, for example. ... Government Interests: This invention was made with government support under Grant Number DE-EE0000272, awarded by the U.S. Department of Energy; the United States federal government, therefore, has certain rights in the invention. Claims: A method of making bismuth titanate nanocubes ... . The present invention relates to formation of nanostructures of sillenite type compounds, such as bismuth titanate nanocubes, via a hydrothermal synthesis process, with the resulting compounds being useful in photovoltaic applications and solar energy conversion for fuel production, for example. (The) material is desirable in energy conversion (photovoltaics), environmental remediation (photodegradation), or solar fuel production (CO2 conversion to value added hydrocarbon chemicals such as alcohols, acids, and ethers), for example (and is) desirable for use in photovoltaic applications and for solar energy conversion CO2 to fuels, for example";

our US Government has more lately begun to expand their support of developments which utilize TiO2 as the foundation for photocatalysts that, in processes driven by solar light energy, convert Carbon Dioxide, in combination with Water, H2O, into various alcohols and hydrocarbons, i.e., "fuels".)

A method of CO2 photoreduction comprising: contacting reactants of CO2 and H2O over a photocatalytic nanocomposite according (the claims herein); reacting the CO2 and H2O over the photocatalytic nanocomposite to produce products including CH4 (Methane).

The method ... wherein the products are substantially free of CO (Carbon Monoxide) gas (and) wherein the CH4 (Methane) has a production rate (as specified).

Background and Field: The invention relates to a photocatalytic nanocomposite, a related method of making the photocatalytic nanocomposite, and a method of using the photocatalytic nanocomposite to covert carbon dioxide into methane.

Photocatalytic materials are drawing significant attention because of their potential for solving environmental and energy problems. 

One potential avenue for reduction of ... CO2 has been CO2 photoreduction using a photocatalyst in which CO2 is reduced ... over the photocatalyst that is activated by UV radiation. To date, titanium dioxide (TiO2) is one of the most studied photocatalysts because it has shown the most efficient photocatalytic activity, highest stability, low cost, as well as low toxicity. In the photocatalytic reaction, electrons and holes are produced from TiO2 under UV irradiation. The electrons and holes subsequently interact with reactants (including CO2) to form the products.

However, CO2 photoreduction has only been performed using titanium dioxide (TiO2) with limited or qualified success. One of the problems in using unmodified TiO2 as a photocatalyst is that electron and hole recombination leads to low photoconversion efficiency. Hence, a continued need exists for a photocatalyst that improves the kinetics of a photoreduction reaction of CO2.

Summary: According to one aspect of the invention, a photocatalytic nanocomposite is provided that includes a reduced graphite oxide, a photocatalytic metal oxide in nanoparticle form, wherein the photocatalytic metal oxide in nanoparticle form is dispersed in the reduced graphite oxide. The photocatalytic metal oxide may be TiO2 and may be in a mixed phase form including rutile and anatase. The reduced graphite oxide may be a powder.

(The above "rutile" and "anatase", as we've explained in earlier reports concerning these sorts of uses for Titanium Dioxide, are just different mineralogical crystalline forms in which Titanate can occur. They are neither rare nor exotic and are well-understood by mineralogists, chemists, etc. We'll note that the catalyst is specified as well to consist of some organic compounds, which themselves are known to organic chemists and can be easily synthesized. One of the specified organic compounds perhaps more familiar to the general public is "propylene"; and, although it is a hydrocarbon compound itself of some value, keep in mind that it serves as a part of the catalyst, and, thus, isn't used up or consumed to any appreciable extent in the solar-powered CO2-to-Methane reactions.)

According to another aspect of the invention, a method of making a photocatalytic nanocomposite of this type is provided. The method of making a photocatalytic nanocomposite includes oxidizing graphite to form a reduced graphite oxide and mixing the reduced graphite oxide with TiO2 nanoparticles to form the photocatalytic nanocomposite. The reduced graphite oxide may be functionalized with a NH2-terminated ionic liquid to form an ionic liquid functionalized reduced graphite oxide before the step of mixing.

According to still another aspect of this invention a method of CO2 photoreduction is provided. The method of CO2 photoreduction includes contacting reactants of CO2 and H2O over a photocatalytic nanocomposite of the type described herein and reacting the CO2 and H2O over the photocatalytic nanocomposite to produce products including CH4.

(Described and illustrated experimental) results show that the regenerated (photocatalyst of the present invention) can produce an almost identical amount of CH4 (Methane) at the same irradiation times (as virgin photocatalyst).

These preliminary results suggest that the (disclosed) TiO2 catalyst can be regenerated and effectively reused in CO2 photoreduction.

This result is significant in that it signifies the real-world application of this material in CO2 photoreduction. The CH4 (Methane) production rate (observed and specified) is about 20-30 times higher as compared to the highest CH4 production rate using other modified TiO2 structure reported in the literature."

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There you have it: In a project funded with our tax money, accomplished Arizona State University scientists claim that they have developed a catalyst that will enable the high-rate "photoreduction" of Carbon Dioxide and Water vapor into substitute natural gas Methane, CH4.

And, we remind you, that, as seen for only one example in our report of:

Pittsburgh 1941 CO2 + Methane = Hydrocarbon Syngas | Research & Development | News; concerning: "United States Patent 2,266,989 - Manufacture of a Gas from CO2 and Methane;1941; Assignee: Koppers Company, Pittsburgh, PA; Abstract: The present invention relates to the manufacture of gases suitable for the synthesis of higher hydrocarbons or the like, said gases containing definite volumes of carbon monoxide and hydrogen in a certain proportion, by reacting on methane ... with carbon dioxide or a mixture of carbon dioxide and steam, so that the methane ... is decomposed into hydrogen and carbon monoxide. ... In order to obtain a gas in the proportion of one volume carbon monoxide to one volume hydrogen, the methane according to the present invention is converted ... by the use of carbon dioxide principally in accordance with the ... reaction: CH4 + CO2 = 2CO + H2. (Such a product gas mixture) is especially suitable for the synthesis of hydrocarbons";

it has been known for a very long time, that, once we have Methane, as synthesized via the process of our subject herein, "United States Patent Application 20140131192 - Ionic Liquid Functionalized Reduced Graphite Oxide / TiO2 Nanocomposite for Conversion of CO2 to CH4", in reactions which could be powered by solar radiation, from Carbon Dioxide, we can then react that CO2-based Methane with even more Carbon Dioxide, and thereby form a syngas blend of "hydrogen and carbon monoxide", which would be "especially suitable", via perhaps the nearly-ancient Fischer-Tropsch process, "for the synthesis of hydrocarbons".

Again, it is demonstrated:

Carbon Dioxide, as it is co-produced - - in a small way relative to some all-natural and un-taxable sources of it's emission, such as the Earth's inexorable processes of planetary volcanism - - during our economically essential use of Coal in the generation of truly abundant and truly affordable electric power, is a valuable raw material resource.

We can, according herein to scientists at Arizona State University, in an official Disclosure published just today, reclaim Carbon Dioxide from whatever handy source, and, then, in a process driven by freely-available sunlight, and requiring only Water as an additional raw material, we can convert that Carbon Dioxide into substitute, fracking-free, natural gas Methane.

 


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