United States Patent Application: 0130252798

Exactly four years ago today, we first made report of the research that likely laid the groundwork for the United States Patent Application, which was published by the US Patent and Trademark Office first thing this morning, that we enclose in this dispatch, wherein catalysts are disclosed that enable the conversion of Carbon Dioxide into Methanol, in photosynthetic reactions powered by visible light.

As seen, from September 26, 2009, in:

West Virginia Coal Association | Taiwan Recycles CO2 | Research & Development; concerning: "'Synergistic Catalysis of Carbon Dioxide Hydrogenation into Methanol'; Authors: Wang, J.B.; Lee, H.K.; Huang, T.J; I-Shou University, Kaohsiung, Taiwan, ROC (and) National Tsing Hua University, Hsinchu, Taiwan, ROC; Source: Catalysis Letters, Volume 83, Numbers 1-2, October 2002 , pp. 79-86(8); Abstract: Methanol synthesis from carbon dioxide hydrogenation was studied over ceria/ -alumina- and yttria-doped ceria (YDC)/ -alumina-supported copper oxide catalysts to seek insight into the catalysis at metal–support interfaces. It was found that, in comparison with Cu/ -Al2O3, the Cu/CeO2/ -Al2O3 -Al2O3 catalysts exhibited substantial enhancement in activity and selectivity toward methanol formation. The extent of enhancement was augmented by increased ceria loading on -alumina and with increased yttria doping into ceria. The enhancement is inferred to result from the synergistic effect between copper oxide and surface oxygen vacancies of ceria";

scientists at two of Taiwan's, the Republic of China's, universities had devised catalysts that promoted the hydrogenation of Carbon Dioxide into, at least, the fuel alcohol, Methanol.

Further, as we reported earlier this year, via:

West Virginia Coal Association | Taiwan Converts CO2 into Plastics Raw Material | Research & Development; concerning: "US Patent Application 20130035497 - Manufacturing Cyclic Carbonate from Carbon Dioxide; February, 2013; Inventor: Shiey-Shiun Horng, Taiwan; (Presumed eventual Assignee of Rights, based on other references: I-Shou University, Taiwan); Abstract: A method of manufacturing cyclic carbonate with carbon dioxide";

the CO2-utilization R&D efforts at Taiwan's I-Shou University, who partnered in the earlier research with Tsing Hua University, continued, and led to the development of technology wherein Carbon Dioxide can be converted into chemical compounds valuable in the synthesis of certain high-performance plastics.

And, herein, as excerpted from the initial link in this dispatch, we see what might represent the culmination, at Tsing Hua University, of the specific research about which we first reported back in 2009, wherein, in a process powered by what we can take to be sunlight, CO2, as recovered from whatever handy source, is converted into Methanol:

"US Patent Application 20130252798 - Metallic Sulfide Photocatalyst for Carbon Dioxide Reduction

METALLIC SULFIDE PHOTOCATALYST FOR CARBON DIOXIDE REDUCTION AND THE PREPARATION FOR THE SAME - NATIONAL TSING HUA UNIVERSITY

Date: September 26, 2013

Inventors: Yong-Chien Ling and Jen-Yu Liu, Taiwan

Assignee: National Tsing Hua University, Taiwan

(We'll interrupt here to provide a little background. First of all, as can be learned via:

Taiwan - Wikipedia, the free encyclopedia; Taiwan's - - (aka "Republic of China", or "ROC", as opposed to the much larger mainland People's Republic of China, "PRC", which was once known simply as an island called Formosa) - - position in the international community is a little complicated. However, as the Wikipedia reports: "Taiwan (has) evolved into a multi-party democracy with universal suffrage" and is now the "19th-largest economy in the world, its advanced technology industry" playing "a key role in the global economy. Taiwan is ranked highly in terms of freedom of the press, health care, public education, economic freedom, and human development".

Further, as seen in:

National Tsing Hua University - Wikipedia, the free encyclopedia; the National Tsing Hua University is "recognized internationally" and is comprised of "7 colleges, 17 departments and 22 independent graduate institutes";

and, the home of these developments is, thus, a very credible institution of higher learning.)

Abstract: Disclosed are the metallic sulfide photocatalyst and its preparation method. The photocatalyst includes at least one soluble metallic salt and a sulfide (as specified). The photocatalyst is afforded by reacting the sulfide with the at least one soluble metallic salt dissolved in the complexing agent. Additionally, the photocatalyst further is customized with co-catalyst such as RuCl to form Ru-carried metallic sulfide photocatalyst. The metallic sulfide photocatalyst and Ru-carried metallic sulfide photocatalyst are capable of effectively reducing CO2 to CH3OH under the visible light illumination.

 

(First, the "Ru", Ruthenium, needed is a Platinum Group metal, and there isn't a lot of it around; and, it ain't cheap. That said, we do have a few deposits in the US Rockies that could, if needed, be exploited, although they're not being currently mined. Otherwise, our good friends in Canada already produce a fair amount of it as a byproduct of Nickel and Copper mining in Ontario. The plus is, that, once we have it, we have it; it serves as a catalyst and isn't used up or consumed in any appreciable way, even though it might have to be re-refined after some period of use. Second, "CH3OH" is Methanol, as is made clear further on.)

Claims: A metallic sulfide, comprising: a dissoluble metallic salt being selected from a group consisting of a dissoluble transition metallic salt, a dissoluble post-transition metallic salt, a dissoluble metalloid salt and a combination thereof; and a sulfide (as specified) wherein the dissoluble transition metallic salt is selected from a group consisting of a dissoluble cobalt salt, a dissoluble nickel salt, a dissoluble copper salt, a dissoluble zinc salt, a dissoluble silver salt and a combination thereof (and) wherein the dissoluble post-transition metallic salt is selected from a group consisting of a dissoluble indium salt, a dissoluble tin salt, a dissoluble bismuth salt and a combination thereof (and) wherein the dissoluble metalloid salt is a dissoluble antimony salt.

(Complicated, we know, but, all of it is available and not really too exotic in the final analysis. Note that "cobalt", "nickel" and "copper" would all be associated with the "ruthenium" which is also needed in, as we suggested, Canada's northern Ontario commercial deposits.)

A preparation method of a metallic sulfide (as detailed).

(The full Claims go into the chemical processing specifics of how the components of the catalyst are to be prepared and blended, which is well beyond our scope of interest herein.)

Background and Field: The present invention relates to a photocatalyst. In particular, the present invention relates to a metallic sulfide photocatalyst for reducing carbon dioxide (CO2) to reproduce methanol (CH3OH) and the preparation method thereof. 

The principle of photocatalytic CO2 reduction to CH3OH lies in that the catalyst is illuminated and excited with light with a specific energy, to reproduce the electron/hole pair. The electrons migrate to the surface of catalyst and reduce H2O to hydrogen, formic acid, formaldehyde, CH3OH and so on via a series of reactions, and holes are consumed by the sacrificial agent in the system. The key point for photocatalytic CO2 reduction to CH3OH is to prepare a photocatalyst having adequate conductivity band and valence band for visible light illumination.

Summary: In the present invention, the metallic compound reacts with sulfuric compound to form the metallic sulfide photocatalyst, which is able to reduce CO2 and reproduce methanol (CH3OH) after the absorption of sunlight or visible light.

The photocatalysis driven by the metallic sulfide photocatalyst of the present invention also can be proceeded to decompose organic compounds (e.g. organic acid such as acetic acid, etc.), to decompose NOx (and) to decompose environmental pollutants.

The metallic sulfide photocatalyst of the present invention has an excellent absorption activity in visible light, ensures that the energy in the VIS spectrum can be adequately used by the photocatalyst. ... Therefore, the metallic sulfide photocatalyst has high photoreduction CO2 activity towards CH3OH reproduction under visible light illumination, and high-temperature conditions and high-energy consumption are unnecessary."

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We've been compelled to edit our excerpts in the extreme, since the bulk of the Disclosure, as we indicated in an inserted comment above, is given over to full description of the chemical reactions and processes entailed in the formulation of the photocatalyst, which, once completely formulated, is able to, in reactions driven by "sunlight or visible light", facilitate the conversion of CO2, along with H2O, into Methanol, in reactions where "high-temperature conditions and high-energy consumption are unnecessary".

And, we'll again remind you, that, as seen for one example in:

West Virginia Coal Association | ExxonMobil Coal to Methanol to Gasoline | Research & Development; concerning both: "United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification; 1982; Exxon Research and Engineering Company; Abstract: Methanol is produced by gasifying a carbonaceous feed material with steam (and) wherein said carbonaceous feed material comprises coal"; and: "United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Mobil Oil Corporation; Abstract: The conversion of methanol to gasoline";

once we have Methanol, as synthesized from one or the other of our abundant natural resources, whether Coal or, as herein, Carbon Dioxide, the technology exists to convert that Methanol directly into the stuff we're squandering our national US wealth to buy from some folks, OPEC, we really don't see eye-to-eye with all that much.

We further remind you that, as seen in:

West Virginia Coal Association | USDOE Sunlight Converts CO2 into Methane | Research & Development; concerning: "US Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation; March 28, 2013; Assignee: UChicago Argonne, LLC, Chicago (USDOE); Abstract: In one preferred embodiment, a photocatalyst for conversion of carbon dioxide and water to a hydrocarbon ... . Government Interests: The United States Government has rights in this invention pursuant to Contract No. DE-AC02-06CH11357 between the United States Government and UChicago Argonne, LLC representing Argonne National Laboratory. This invention relates to the energy efficient photocatalytic conversion of carbon dioxide gas and water vapor to methane ... particularly promoted by sunlight";

this Taiwan development mirrors other very current sunlight-driven CO2-recycling accomplishments, that seem very similar, achieved by some folks a little closer to home, wherein a slightly different product is evolved.

And, both perhaps arose from work initiated decades ago, exemplified by the technology disclosed in our report of:

West Virginia Coal Association | Big Oil CO2 to Methanol Photosynthesis | Research & Development; concerning: "United States Patent 4,427,508 - Light Driven Photocatalytic Process; 1984; Assignee: Atlantic Richfield Company; Abstract: A method for the light driven photocatalytic reduction of carbon dioxide ... to one or more compounds which comprises contacting silicon with the carbon dioxide ... in the presence of light. Claims: A method for the light driven photocatalytic reduction of carbon dioxide (to other compounds, and, wherein) the energy of reduction is essentially supplied by ... light (and) wherein said light is one of artificial light, sunlight, or a combination thereof. (Compounds produced include) methanol ... and methane";

wherein "sunlight" is seen to be able to convert CO2 into both Methane and the product of our subject herein, "US Patent Application 20130252798 - Metallic Sulfide Photocatalyst for Carbon Dioxide Reduction", Methanol.

As confirmed once more herein, we can harness environmental energy, specifically plain old sunlight, in a process that converts Carbon Dioxide, and H2O, into a fuel alcohol that is also a valuable raw material for the further synthesis of various hydrocarbons, including fuels, such as Gasoline, and certain plastics.

That would be in lieu of, of course, Cap and Trade Carbon taxes, which, as described in:

American Clean Energy and Security Act - Ask.com Encyclopedia; would comprise the "largest tax hike in world history".


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