United States Patent: 8709304

We remind you, that, among the many amazing achievements now being seen around the world, with none of them being reported openly and publicly to us here in United States Coal Country - - where the implications of those achievements could be of profound direct benefit to the economic and environmental security of the United States of America, and of indirect benefit to our essential United States Coal-fired power generation industries - - are those wherein it's seen that Carbon Dioxide can be harvested from our environment, or from industrial exhaust gases, and then, in some cases using freely-available environmental energies to drive the processes, that Carbon Dioxide can be converted into any and all forms of hydrocarbon gases and liquids.

 

Examples of such developments are discussed, for one example, in our report of:

: Saudi Arabia and CO2: The Rich Get Richer | Research & Development | News; which centers on the news story: "'SABIC Unit Plans World’s Largest CO2 Purification Plant'; United Jubail Petrochemical Company, an affiliate of Saudi’s SABIC, has awarded a construction contract for the plant to Germany’s Linde Group. By Aarti Nagraj, August 21, 2013; An affiliate of Saudi Basic Industries Corporation (SABIC) announced that it has awarded a construction contract to build the world’s largest carbon dioxide (CO2) purification and liquefaction plant in the Kingdom. United Jubail Petrochemical Company (United), a manufacturing unit of SABIC, has given the engineering, procurement and construction contract for the project to Germany’s The Linde Group, it said in a statement. ... The plant will be designed to compress and purify about 1,500 tons per day of raw carbon dioxide coming from ethylene glycol plants. The purified gaseous CO2 will then be supplied through pipes to three SABIC-affiliated companies for enhanced methanol and urea production, the statement said. Methanol is a basic commodity for the chemical industry, and urea is used for fertilizer production. The plant will help save an estimated 500,000 tons of CO2 emissions each year, SABIC stated. Yousef Al-Zamel, SABIC executive vice president, Chemicals Strategic Business Unit, said: “It will add to SABIC’s business portfolio of industrial gas products. This is the first of many other similar projects to be executed next year”;

wherein it's seen that Saudi Arabia Basic Industries Corporation, by some reports the largest company headquartered in that part of the world, in concert with the German engineering giant, the Linde Group, is building a factory that will reclaim Carbon Dioxide emitted by petrochemical refineries and then convert that CO2 into such seemingly desirable stuff as fuel alcohol, industrial raw materials, and, even, synthetic petroleum.  

Fortunately, some enlightened entities in the United States are, as well, actively developing Carbon Dioxide recycling technologies, as seen, for one example, in our report of:

Nevada Sunshine Converts "Byproduct" CO2 into Fuel Alcohol | Research & Development | News; which concerns: "United States Patent Application 20130032470 - Systems Including Nanotubular Arrays for Converting Carbon Dioxide to an Organic Compound; 2013; Inventors: Susanta Mohapatra, NV, and Manoranjan Misra, KY; Assignee: The University of Nevada; Abstract: A system including nanostructure arrays for converting carbon dioxide to an organic compound, e.g., methanol, which does so, for examplewithout any external electric energy. In one embodiment, the system for converting carbon dioxide to an organic compound includes an array of nanotubes, which include nanoparticles of an electron mediator, e.g. palladium, dispersed on a surface of the nanotubes, and an electrically conductive fluid. The array of nanotubes is at least partially immersed in the electrically conductive fluid. The system further includes a light source that irradiates the array of nanotubes, a source of carbon dioxide, and an inlet for delivering the carbon dioxide to the electrically conductive fluid whereat at least a portion of the carbon dioxide is converted to a different organic compound, such as methanol, via contact with an irradiated array of nanotubes. In one example, the array is an ordered array of titania nanotubes";

wherein University of Nevada scientists define a route of photosynthesizing Methanol from Carbon Dioxide, with Methanol being one of the key products Saudi Arabia intends to synthesize from their own CO2.

Another technology related to the light-driven consumption of Carbon Dioxide in the photocatalytic synthesis of hydrocarbons and other compounds has also been developed by the University of Nevada, as seen in our report of:

Nevada Sunshine Converts More CO2 into Solar Fuels | Research & Development | News; concerning: "United States Patent Application 20110155971 - Hydrothermal Synthesis of Nanocubes of Sillenite Type Compounds for Photovoltaic Applications and Solar Energy Conversion of Carbon Dioxide to Fuels; 2011; Inventors: Vaidyanathan Subramanian and Sankaran Murugesan, NV and TX; Assignee: University of Nevada, Reno; Abstract: The present invention relates to formation of nanocubes of sillenite type compounds ... with the resulting compound(s) having multifunctional properties such as being useful in solar energy conversion, environmental remediation, and/or energy storage, for example. The present invention relates to formation of nanostructures of sillenite type compounds, such as bismuth titanate, ... Such nanotubes are ... 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)... (and) for solar energy conversion (of) CO2 to fuels."

And, herein we learn, that, just days ago, technical experts in the employ of our United States Government not only formally confirmed the technical validity of the above Solar CO2-to-Fuels technology, but disclosed some additional information, as well, through their allowance and issuance of, as excerpted from the initial link in this dispatch:

"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

Hydrothermal synthesis of nanocubes of sillenite type compounds for photovoltaic applications and solar energy conversion of c

Date: 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. In one embodiment, a hydrothermal method is disclosed that transforms nanoparticles of TiO2 to bismuth titanate, i.e., Bi12TiO20, nanocubes, optionally loaded with palladium nanoparticles. The method includes reacting titanium dioxide nanotubes with a bismuth salt in an acidic bath at a temperature sufficient and for a time sufficient to form bismuth titanate crystals, which are subsequently annealed to form bismuth titanate nanocubes. After annealing, the bismuth titanate nanocubes may be optionally loaded with nano-sized metal particles, e.g., nanosized palladium particles.

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.

(The above means, US Coal Country friends and neighbors, that we, all of us, through our taxes, paid to have this CO2-to-Fuel technology developed; and, that we, all of us, as individuals own at least an itty-bitty piece of it. When, do you suppose, we were all going to be told about it? Before or after parasitic Cap and Trade Carbon taxes have been implemented to leach our vital and productive Coal-fired power generation industries? Before or after Saudi Arabian tankers full of hydrocarbons made from Carbon Dioxide, as in our earlier report cited above, have started sailing into New York Harbor, under the nose of the Statue of Liberty?) .

Claims: A method of making bismuth titanate nanocubes comprising: reacting titanium dioxide nanotubes with a bismuth salt in an acidic bath at a temperature sufficient and for a time sufficient to form bismuth titanate crystals having the formula Bi12TiO20, where Bi is bismuth; Ti is titanium ... and O is oxygen; and annealing the bismuth titanate crystals to form bismuth titanate nanocubes (via the method specified and described, and) loading the bismuth titanate nanocubes with nano-sized metal particles (including) palladium (Pd) nanosized metal particles. 

A method of making bismuth titanate nanocubes (as specified in terms of temperature and time).

Background and Field: 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. 

(Extensively) studied and used as photocatalysts to harvest solar energy are nanoparticles of titanium dioxide (TiO2). TiO2 nanoparticles have shown very good stability over a wide pH range and are compatible with other materials, environmentally friendly, inexpensive, and non-toxic. However, interfacial grain boundaries in films prepared from TiO2 nanoparticles have been known to contribute to reducing charge transport by functioning as recombination centers. Recently, the synthesis of TiO2 specifically in the form of hollow nanotubes by anodization of a titanium foil has been demonstrated ... . Such nanotubes are generally produced by anodic oxidation in various electrolytes. Notably, the absence of grain boundaries in the resulting nanotubes favors efficient transport of photogenerated electrons. And since the TiO2 nanotubes are electrically well connected and anchored firmly on an underlying titanium substrate as a raw material for preparing sillenite type compounds, 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. 

(It) would be beneficial to provide a simple synthesis process for preparing nanostructures of sillenite type compounds, including Bi12TiO20 nanotubes, from corresponding oxides, e.g., TiO2, which overcomes the (known) drawbacks (of establised art), with the resulting compounds being desirable for use in photovoltaic applications and for solar energy conversion CO2 to fuels, for example

Discussion and Summary: (Disclosed) herein is a method for nanocube synthesis of sillenite type compounds of the general formula (I), including Bi12TiO20 nanocube synthesis and its photoelectrochemical properties. The resulting nanocubes, including Bi2TiO20 nanocubes, can be useful for solar energy coversion to electricity (photovoltaic devices) and CO2 conversion to value added fuels, such as to harvest solar energy, as well as for photocatalysis applications, for example".

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The full Disclosure continues at considerable length to further describe and expose different aspects and examples of the technology.

Most of the specific examples they chose to include describe the photo-conversion of Carbon Dioxide and H2O into formic acid; which is, as we've described in previous reports, a useful industrial compound, but which, in and of itself, isn't particularly exciting. Although, as seen for one example in:

Flue gas desulfurization with formic acid from BASF - BASF Intermediates;

it could have intriguing Coal Country applications.

And, technologies are being and have been developed for the direct electro-catalytic conversion of formic acid into more useful compounds, like Methanol and Formaldehyde. See, for example:

CATALYTIC CONVERSION OF FORMIC ACID TO METHANOL WITH Cu AND Al UNDER HYDROTHERMAL CONDITIONS | Yao | BioResources .

 
However, that only relates to the specific examples illustrated for the use of the "Sillenite Type Compounds" in the full Disclosure of our subject, "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".

As in our report of:

Panasonic 2013 CO2 to Methane, Formic Acid and Carbon Monoxide | Research & Development | News; "United States Patent 8,414,758 - Method for Reducing Carbon Dioxide; 2013; Assignee: Panasonic Corporation, Osaka (Japan); Abstract: A device for reducing carbon dioxide (and, a) method for reducing carbon dioxide by using a device for reducing carbon dioxide includes steps of providing carbon dioxide into the cathode solution, and irradiating at least part of the nitride semiconductor region and the metal layer with a light having a wavelength of 250 nanometers to 400 nanometers, thereby reducing the carbon dioxide contained in the cathode electrolyte solution. ... The method ... wherein ... formic acid (and/or) carbon monoxide (and/or) methane is obtained";

other, perhaps more intriguing, compounds can be made from Carbon Dioxide in addition to "formic acid", but in this case using the basic catalyst disclosed by "United States Patent 8,709,304". And, if you take the time to examine the full Disclosure, you'll see that the University of Nevada goes into detailed exposition about various other metals that can be loaded into/onto their "sillenite type compounds", in addition to or instead of the specified "palladium", with implications for adjusting the types and distributions of products derived from their  "Photovoltaic" chemical reduction of Carbon Dioxide; some of which products, including Methanol and Methane, could indeed be labeled as "Fuels". And, those various "sillenite type compounds" of our subject could well find application in conjunction with the University of Nevada's technology disclosed in our above-cited report, concerning:

"United States Patent Application 20130032470 - Systems Including Nanotubular Arrays for Converting Carbon Dioxide to an Organic Compound; 2013; Assignee: The University of Nevada; Abstract: A system including nanostructure arrays for converting carbon dioxide to an organic compound, e.g., methanol, which does so, for examplewithout any external electric energy".


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