United States Patent Application: 0130192975
We've documented many times for you over recent years that the art and science of harnessing freely available Solar heat and/or light energy to effect the catalyzed conversion of Carbon Dioxide, as is so fortuitously co-produced by our combustion of Coal during the generation of truly abundant and truly affordable electric power from our by far most abundant fossil energy resource, and Hydrogen, as extracted, again using environmental energy to drive the process, from plain old Water, into various hydrocarbons and alcohols, such as Methanol and substitute natural gas Methane, has been evolving and improving around the world.
Aside from the numerous substantial and credible corporations that have been at work developing such technology, it's reality is confirmed by the active participation of our own United States Government in that development, as seen for only one, but very recent, example 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; March 28, 2013; Assignee: UChicago Argonne, LLC, Chicago; Abstract: In one preferred embodiment, a photocatalyst for conversion of carbon dioxide and water to a hydrocarbon and oxygen comprises at least one nanoparticulate metal or metal oxide material that is substantially free of a carbon coating, prepared by heating a metal-containing precursor compound in a sealed reactor under a pressure autogenically generated by dissociation of the precursor material in the sealed reactor at a temperature of at least about 600 C to form a nanoparticulate carbon-coated metal or metal oxide material, and subsequently substantially removing the carbon coating. The precursor material comprises a solid, solvent-free salt comprising a metal ion and at least one thermally decomposable carbon- and oxygen-containing counter-ion, and the metal of the salt is selected from the group consisting of Manganese, Titanium, Tin, Vanadium, Iron, Zinc, Zirconium, Molybdenum, Niobium, Tungsten, Europium, Lanthanum, Cerium, Indium, and Silicon. 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 ... . This invention relates to the energy efficient photocatalytic conversion of carbon dioxide gas and water vapor to methane".
Note, in the above, the specification of "Cerium" as one of the components of a "photocatalyst" capable of promoting the Solar-driven conversion of "carbon dioxide gas and water vapor to methane". It is one option; and, as we will be documenting in some reports to follow, it is apparently so effective that a great deal of related work has been devoted to the refinement and application of Cerium-based catalysts for such "Solar Fuel" production technologies.
However, as seen in our report of:
West Virginia Coal Association | The USDOE and New Jersey Convert CO2 into Ethanol | Research & Development; concerning: "United States Patent Application 20130199937 - Reducing Carbon Dioxide to Products; 2013; Assignee: Liquid Light, Inc., NJ; Abstract: A method reducing carbon dioxide to one or more products ... . Government Interests: This invention was made with government support under Grant DE-SC0006201 awarded by the Department of Energy. The government has certain rights in the invention. Claims: A method for reducing carbon dioxide to one or more products, comprising: (A) bubbling said carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell, wherein:(i) said divided electrochemical cell comprises an anode in a first cell compartment and a cathode in a second cell compartment, (ii) said cathode reducing said carbon dioxide into said products, and: (iii) said cathode is selected from the group consisting of Al, Au, Ag, Bi, C, Cd, Co, Cr, Cu, a Cu alloy, Ga, Hg, In, Mo, Nb, Ni, NiCo2O4, a Ni alloy, a Ni--Fe alloy, Pb, Rh, Sn, a Sn alloy, Ti, V, W, Zn, Nichrome, austenitic steel, duplex steel, ferritic steel, martensitic steel, stainless steel ... and mixtures thereof";many other metallic and semi-metallic elements can serve in the needed photo-catalytic compositions, as well; and, we call your attention herein specifically to "Ga", Gallium; which, as can be learned via:
Gallium - Wikipedia, the free encyclopedia; "Beginning with its discovery in 1875 through the era of semiconductors, gallium was used primarily as an agent to make alloys that melt at low temperatures. Then, gallium became useful in semiconductors, including as a dopant. Today, nearly all gallium is used in electronics. Gallium arsenide, the primary chemical compound of gallium in electronics, is used in microwave circuits, high-speed switching circuits, and infrared circuits ... . Multijunction photovoltaic cells, developed for satellite power applications, are made (from) gallium arsenide (and other gallium compunds). ... Gallium is also a component in photovoltaic compounds ... for use in solar panels as a cost-efficient alternative to crystalline silicon";
has a variety of high-tech uses in it's role as a "semiconductor", especially, and, as we will see, as a "component in photovoltaic compounds".
And, herein, we see that scientists in South Korea - - where, as seen for only one example in our report of:
West Virginia Coal Association | Korea CO2 to Methanol & Dimethyl Ether | Research & Development; concerning: "United States Patent 6,248.795 - Dimethyl Ether and Methanol from Carbon Dioxide; 2001; Assignee: Korea Research Institute of Chemical Technology; Abstract: This invention relates to the process of preparing from carbon dioxide a mixture of dimethyl ether and methanol which are useful as clean fuel or raw materials in the chemical industry. More particularly, this invention relates to the process of preparing dimethyl ether and methanol in high yield without by-products such as hydrocarbons by means of chemical conversion of carbon dioxide";
they do take the concept of Carbon Dioxide being a valuable raw material resource seriously - - have improved upon methods of manufacturing what we would call "artificial photosynthesis" catalysts, from Gallium, for the light-driven conversion of Carbon Dioxide into substitute natural gas Methane.
Comment follows excerpts from the initial link in this dispatch to:
"United States Patent Application 20130192975 - Method of Manufacturing a Porous Gallium (III) Oxide Photocatalyst for Preparation of Hydrocarbons
August 1, 2013
Inventors: Jeung-Ku Kang, et. al., Korea
Assignee: Korea Advanced Institute of Science and Technology, Daejeon, Korea
Abstract: The present invention relates to preparation of porous gallium (III) oxide (Ga2O3) photocatalyst for production of hydrocarbons (and) a process of producing hydrocarbons using the porous gallium oxide photocatalyst for production of hydrocarbons.
(Note the similarity in tone and concept to the above-cited USDOE's "United States Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation")
Claims: A method of manufacturing a porous gallium (III) oxide photocatalyst for production of hydrocarbons, comprising: adding a base and a surfactant to a solvent and agitating the mixture to prepare a solution containing micelles formed therein; adding a solution containing a gallium precursor to the micelle-containing solution to conduct a reaction; and washing and drying a precipitate obtained by filtering reactants after the reaction, and heating the precipitate to remove the micelles from a surface and an inner part of the precipitate, followed by forming pores therein (and as further described).The method ... wherein the hydrocarbons comprise aliphatic hydrocarbons having 1 to 4 carbon atoms (and) wherein the hydrocarbons comprise methane.
A porous gallium (III) oxide photocatalyst for production of hydrocarbons (manufactured as described) wherein the porous gallium (III) oxide photocatalyst is prepared in a rod shape having pores with a diameter (and) a specific surface area (as specified).
A method for production of hydrocarbons, comprising reacting the porous gallium (III) oxide photocatalyst manufactured by the method (disclosed) with CO2 and water as raw materials under a light source (and)
wherein the hydrocarbons (produced) comprise methane.
(We'll interrupt to remind you, that, as seen for only one example in our report of:
West Virginia Coal Association | China Extracts High-Tech Metal from Coal Ash | Research & Development; concerning:"'Method For Extracting Gallium From Fly Ash'; Publication No.: WO/2011/134402; International Patent Application No.: PCT/CN2011/073392; April 27, 2011; Applicant: China Shenhua Energy Company, Beijing; Abstract: Disclosed is a method for extracting gallium from fly ash, which comprises the following steps: crushing the fly ash and removing Fe by magnetic separation; then dissolving it by using hydrochloric acid to obtain hydrochloric acid leachate; adsorbing gallium in the hydrochloric acid leachate with macroporous cation resin, followed by eluting to obtain the eluent containing gallium; adding masking agent to mask ferric ion to obtain the eluent containing gallium after masking; adsorbing gallium in the eluent containing gallium after masking with macroporous cation resin, followed by eluting to obtain secondary eluent; adding sodium hydroxide solution into the secondary eluent to react; filtering and removing precipitate after reaction, and then concentrating the filtrate and electrolyzing to obtain metal gallium. The method simplifies the process and improves extraction yield of gallium";we can likely find enough Gallium to support this CO2-to-Methane technology right here in the general neighborhood of US Coal Country.)
Background and Field: The present invention relates to a method of manufacturing a porous gallium (III) oxide (Ga2O3) photocatalyst for production of hydrocarbons, and more particularly, to a method of manufacturing a porous gallium (III) oxide photocatalyst for production of hydrocarbons, comprising: adding a base and a surfactant to a solvent and agitating the mixture to prepare a solution containing micelles formed therein; adding a solution containing a gallium precursor to the micelle-containing solution to conduct a reaction; and washing and drying a precipitate obtained by filtering reactants after the reaction, and heating the precipitate to remove the micelles from a surface and an inner part of the precipitate, followed by forming pores therein.
The present invention also relates to a porous gallium oxide photocatalyst for production of hydrocarbons, manufactured by the foregoing method, and a process of producing hydrocarbons using the porous gallium oxide photoctalyst for production of hydrocarbons, manufactured by the foregoing method.
The hydrocarbons described above may include hydrocarbons having 1 to 4 carbon atoms, preferably, aliphatic hydrocarbons having 1 to 4 carbon atoms, and more preferably, methane.
Grimes et al. have disclosed photo-synthesis wherein titanium dioxide nanotubes (TiO2 nanotubes) synthesized through anodization is used to generate methane from CO2 and water (High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon fuels, Nano Lett., 2009, 9,731).
(Concerning the above citation of "Grimes et al", see, for only one example, our report of:
West Virginia Coal Association | Penn State Solar CO2 + H2O = Methane | Research & Development; concerning: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; Oomman K. Varghese, Maggie Paulose, Thomas J. LaTempa, and Craig A. Grimes; Materials Research Institute, The Pennsylvania State University;American Chemical Society, January 2009; Efficient solar conversion of carbon dioxide and water vapor to methane and other hydrocarbons is achieved using nitrogen-doped titania nanotube arrays".)Summary: In order to convert carbon dioxide (CO2) to methane using solar energy, it is important to use an excellent photocatalyst. Recently, gallium (III) oxide (Ga2O3) has attracted worldwide attention since it has superior photo-catalytic properties and high reduction potential to render CO2 to be converted to methane.
An object of the present invention is to provide a method of manufacturing a porous gallium (III) oxide (Ga2O3) photocatalyst which can produce hydrocarbons, preferably, aliphatic hydrocarbons having 1 to 4 carbon atoms, and more preferably, methane by using carbon dioxide (CO2) and water under a light source with high reaction efficiency and/or productivity; or, otherwise, which can conduct conversion of the above materials (that is, CO2 and water) to the foregoing, that is, hydrocarbons, preferably, aliphatic hydrocarbons having 1 to 4 carbon atoms, and more preferably, methane.
Another object of the present invention is to provide the porous Ga2O3 photocatalyst for production of hydrocarbons, manufactured by the foregoing method (and) to provide a process of producing hydrocarbons using the porous Ga2O3 photocatalyst for production of hydrocarbons, manufactured by the foregoing method.
The porous Ga2O3 photocatalyst manufactured by the present invention includes pores afforded therein to increase an amount of CO2 adsorption as a product of photo-reaction and, since such a photo-reaction is a reaction occurring at the surface of the Ga2O3 photocatalyst, an increase in CO2 adsorption on the pores present inside the Ga2O3 may contribute to improvement in efficiency of the photo-reaction, thereby rendering hydrocarbons, preferably, aliphatic hydrocarbons having 1 to 4 carbon atoms, and more preferably, methane to be produced in large quantities."
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So, according to the process of our subject herein, "United States Patent Application 20130192975 - Method of Manufacturing a Porous Gallium (III) Oxide Photocatalyst for Preparation of Hydrocarbons", we can expose a mixture of Carbon Dioxide and Water, in contact with the disclosed "Photocatalyst", to "a light source", presumably sunshine, which combination of raw materials, energy and catalyst will cause "methane to be produced in large quantities" - thereby making unnecessary, even unadvisable and counterproductive, certain evils like Cap & Trade carbon taxes and hydrofracking for shale gas.
And, further, we remind you, that, they also know in Korea, as seen for one example in our report of:
West Virginia Coal Association | Korea Receives US CO2 Recycling Patent | Research & Development; concerning: "United States Patent 7,410, 717 - Solid Oxide Fuel Cell for Co-producing Syngas and Electricity by ... Reforming Carbon Dioxide; 2008; Inventor: Dong Ju Moon, et. al.; Assignee: Korea Institute of Science and Technology; Seoul; Abstract: The present invention relates to a solid oxide fuel cell for internal reforming of hydrocarbons and carbon dioxide ... . A solid oxide fuel cell for coproducing syngas and electricity by internal reforming of methane and carbon dioxide ... wherein the feed of CO2 and CH4 to said system is at least partially from a process producing CO2 and CH4 as by-products";
how to, once they have "methane ... produced in large quantities", via the process of "United States Patent Application 20130192975 - Method of Manufacturing a Porous Gallium (III) Oxide Photocatalyst for Preparation of Hydrocarbons", from Sunlight, Water and Carbon Dioxide, react that CO2-based Methane, "CH4", with even more Carbon Dioxide, and thereby make both "electricity" and "syngas", a blend of Carbon Monoxide and Hydrogen suitable for the subsequent catalytic synthesis, as via for one example the nearly ancient Fischer-Tropsch process, of both gaseous and liquid hydrocarbon fuels.
In sum, they know, in Korea, how to, starting with nothing but Water and Carbon Dioxide as the raw materials and using nothing but sunlight to drive the process, synthesize Methane "in large quantities" from that Water and that Carbon Dioxide.
And, before monstrosities and exploitations like Cap & Trade carbon taxes or, may Heaven forbid it, another Middle East hydrocarbon war, lurch one step closer to being made manifest in our world, we'll close with a quote intended for and directed to the half-dozen or so Coal Country journalists who are among the primary addressees of these humble research reports:
"As a matter of honor, one man owes it to another to manifest the truth." - Thomas Aquinas