United States Patent Application: 0110155971
As seen most recently in our report of:
West Virginia Coal Association | USDOE Sunlight Converts CO2 into Methane | Research & Development; concerning: "US Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation; 2013; Inventor: Brian Ingram, et. al., IL and TN; Assignee: UChicago Argonne, LLC, Chicago; Abstract: In one preferred embodiment, a photocatalyst for conversion of carbon dioxide and water to a hydrocarbon and oxygen ... . 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. Claims: A photocatalyst for conversion of carbon dioxide and water into a hydrocarbon and oxygen (and, a) method of converting carbon dioxide and water into a hydrocarbon and oxygen comprising exposing a gaseous mixture of carbon dioxide and water to sun light in the presence of a photocatalyst ... . This invention relates to the energy efficient photocatalytic conversion of carbon dioxide gas and water vapor to methane and other hydrocarbon fuels, particularly promoted by sunlight";
progress continues to be made in the development of what is becoming more broadly known as "Solar Fuel" technology, wherein the energy of simple sunlight is harnessed to drive the conversion of "carbon dioxide and water into a hydrocarbon and oxygen" by the seemingly-straightforward proposition of "exposing a gaseous mixture of carbon dioxide and water to sun light in the presence of a photocatalyst".
We see something like that going on all around us in the natural world every day, of course, through the process of photosynthesis being exploited by every green plant on Earth.
Not only is progress in general being made in the development of such technologies - - technologies which would, of course, render obsolete and almost criminally irresponsible both our continued reliance on OPEC for hydrocarbon fuels and the imposition of anything like Cap and Trade carbon taxes on our economically essential Coal-based power-generation industries - - but, the technologies are becoming so refined, so highly developed and evolved in their details, that the public expositions of them are so complicated, and treat such specific technical minutiae that are components of the overall process, we find ourselves stumped trying to find ways to make cogent, understandable report of them.
That won't stop us from eventually taking a stab at it, of course, especially since some government scientists who once had closer ties both to Coal Country and to the Coal industry are involved in the effort. There are, though, expositions of such Carbon Dioxide-recycling technology wherein, even though the technical minutiae dominate, it's still pretty-darned clear what's going on, which is:
Carbon Dioxide, as recovered from whatever handy source, is being converted, in a process powered by solar light energy, into gaseous and liquid hydrocarbon fuels.
That is the case with the subject of our discourse herein, concerning which we first remind you of our earlier report, now accessible on the West Virginia Coal Association's web site via:
West Virginia Coal Association | Nevada Sunshine Converts "Byproduct" CO2 into Fuel Alcohol | Research & Development; 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 example, without 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 CO2.
As an aside, if any Coal Country journalist should somehow find themselves interested enough to want to learn more about that type of technology, wherein solar energy can be made, through the utility of "titania nanotubes", to convert Carbon Dioxide into an "organic compound such as methanol", but can't justify the cost of a long distance call to Nevada to see how and why Cap and Trade taxes could and should be made unnecessary and counterproductive, we remind you that, as seen in:
West Virginia Coal Association | Penn State Seeks CO2 Recycling Patent | Research & Development; concerning: "US Patent Application 20100213046 - Nanotube ... Photocatalytic Conversion of Carbon Dioxide; 2010; Inventors: Craig Grimes, et. al., PA; Assignee: The Penn State Research Foundation; Abstract: Nitrogen-doped titania nanotubes exhibiting catalytic activity on exposure to any one or more of ultraviolet, visible, and/or infrared radiation, or combinations thereof are disclosed. The nanotube arrays may be co-doped with one or more nonmetals and may further include co-catalyst nanoparticles. Also, methods are disclosed for use of nitrogen-doped titania nanotubes in catalytic conversion of carbon dioxide alone or in admixture with hydrogen-containing gases such as water vapor and/or other reactants as may be present or desirable into products such as hydrocarbons and hydrocarbon-containing products";
some folks a lot closer to home might be able to provide a little insight.
But, in the meantime, we learn herein that the folks out at the University of Nevada have continued to develop their Carbon Dioxide-to-Solar Fuel technology, and developed a variant on the "titania nanotube" solar conversion of CO2 into hydrocarbon fuels.
As seen in excerpts from the initial link in this dispatch to:
"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
Date: June 30, 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, 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 ... 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.
(Note that this technology and process actually seems to use "titanium dioxide nanotubes", as might be described and disclosed in the above-cited Penn State process and technology of "US Patent Application 20100213046 - Nanotube ... Photocatalytic Conversion of Carbon Dioxide", as starting materials with which to make the perhaps more active and more effective palladium-doped "bismuth titanate nanocubes".
Concerning "sillenite", see: http://www.
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 or a fraction thereof between 0 and 1; and O is oxygen; and annealing the bismuth titanate crystals to form bismuth titanate nanocubes.
(Note that our reproduction herein of the "Bi12TiO20" formula might not be entirely accurate. It is a complex crystalline compound with formulaic representations that we, here, especially absent now the services of some of the more chemically-astute folks who used to advise us, aren't competent to interpret. A high school chemistry teacher could no doubt explain it succinctly and clearly, if anyone felt interested enough to call one up and ask.)
The method ... wherein the acidic bath has a pH of 0 to 2 (and) wherein the temperature sufficient is from about 110 to about 175 C (and) wherein the time sufficient is from about 24 hours to about 72 hours.
The method ... wherein the bismuth titanate nanocubes define an elongated cube-like structure having a length of about 200 nm to about 1 micron (and) further comprising, after annealing the bismuth titanate crystals to form bismuth titanate nanocubes, loading the bismuth titanate nanocubes with nano-sized metal particles (and) wherein the nanosized metal particles include palladium (Pd) nanosized metal particles.
(The "palladium" can be fairly expensive; but, it isn't used up or consumed in the process.)
A method of making bismuth titanate nanocubes ... further comprising ... placing the bismuth titanate nanocubes in a metal salt solution and subjecting the mixture to ultrasonication for a time sufficient to load the bismuth titanate nanocubes with the metal salt; and annealing the loaded bismuth titanate nanocubes to reduce the metal salt thereby forming bismuth titanate nanocubes that are loaded with nano-sized metal particles ... nanosized metal particles are palladium (Pd) nanosized metal particles.
(The "Claims" go on to explain how other metals, such as "bismuth, strontium, tin, nickel, aluminum, titanium, iron, silicon, barium, manganese, zinc, cadmium, calcium, copper, cobalt, vanadium, gallium, yittrium, lanthanum, cerium, hafnium, niobium, europium, samarium, or gadolinium" can also be used or included in the basic "general" formula. There are, in other words, options insofar as what materials are needed and how they can be combined, which options can lead to economies or improved efficiencies. The point being that this can probably be accomplished with materials that can be, one way or another, made available just about anywhere.)
Background and Field: The present invention relates to formation of nanostructures of sillenite type compounds, such as bismuth titanate, ... via a hydrothermal synthesis process, with the resulting compounds being useful in photovoltaic applications and solar energy conversion for fuel production, for example.
Also 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. ... Recently, the synthesis of TiO2 specifically in the form of hollow nanotubes by anodization of a titanium foil has been demonstrated ... .
Based on the foregoing, 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 aforementioned drawbacks, with the resulting compounds being desirable for use in photovoltaic applications and for solar energy conversion CO2 to fuels ... .
Summary: In one embodiment, a method of making a bismuth titanate nanocube is provided, which 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 having the formula Bi12TiO20, where Bi is bismuth; Ti is titanium or a fraction thereof between 0 and 1; and O is oxygen. Then the bismuth titanate crystals are 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.
(Illustrations of experimental results) show photocatalytic reduction of carbon dioxide (CO2) over time ... . Typically, reduction of CO2 results in a spectrum of reaction products such as formic acid, formaldehyde, methanol, acetic acid and others."
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The full Disclosure is much more detailed than our excepts might make it seem; and, to reaffirm one of our inserted comments above, it divulges in even greater detail how a variety of elements can be inserted in, or substituted for, the basic Bismuth-Titanium Oxide, with added Palladium, in the photocatalytic formula. But, in sum, simple sunlight, using the "photocatalyst" disclosed herein by the University of Nevada, can drive the conversion of Carbon Dioxide, perhaps as collected via a process like that described in our report of:
West Virginia Coal Association | New Jersey Reclaims CO2 for Hydrocarbon Synthesis | Research & Development; concerning: "United States Patent 8,500,987 - Purification of Carbon Dioxide from a Mixture of Gases; 2013; Assignee: Liquid Light, Inc., NJ";
into stuff like "formaldehyde", which can be further used in the manufacture of a variety of plastic resins and foams, wherein the Carbon Dioxide consumed, via the technology of our subject, "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", would be forever, and productively, "sequestered".
And, the Carbon Dioxide can also be converted into other stuff, like "methanol", which can, as in our report:
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; Assignee: Exxon Research and Engineering Company' Abstract: Methanol is produced by gasifying a carbonaceous feed material with steam ... wherein said carbonaceous feed material comprises coal"; and:
"United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation; Abstract: The conversion of methanol to gasoline boiling products in a plurality of sequentially arranged catalyst beds";
no matter which of our abundant natural resources, whether, as in the process of "United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification", Coal, or, as in the process of our subject herein, Carbon Dioxide, we make the Methanol from, be further directly converted into Gasoline.
As confirmed once more herein:
Carbon Dioxide, as it arises in only a small way, relative to some natural sources of emission, such as the Earth's inexorable processes of planetary volcanism, from our economically essential use of Coal in the generation of truly abundant and truly affordable electric power, can be and should be seen and treated as a valuable raw material resource.