United States Patent: 8716171

If we need more ammo with which to defend Coal Country in the CO2-based "War On Coal", we have it.

The pace of innovation in the productive recycling of Carbon Dioxide, especially in the synthesis of liquid and gaseous hydrocarbon fuels, is increasing dramatically.

There is no longer any doubt that Carbon Dioxide can be efficiently harvested, either from the environment or from industrial exhaust gases, and then be profitably consumed as a primary raw material in the synthesis of hydrocarbons, including both liquid and gaseous hydrocarbon fuels.

 

We were at work on a re-exposition of some older CO2-to-Fuel technologies, which have proven to be the foundations of much more recent CO2 utilization achievements, when the item we bring to you herein was, we think just recently, published on the web by our US Government. We just discovered it.

And, since it pertains directly to current growing concerns about our supply of natural gas, as typified by Methane, and how we obtain it, and how large our reserves of it, really, in fact, are, we elected to interrupt our current line of research to bring it to you.

First, we remind you that, totally unreported to the EPA-beleaguered citizens of United States Coal Country, as can be learned, for only a few examples, via:

http://www.solar-fuels.org/; concerning the international "Solar Fuels Institute", in which the USDOE is an active participant; and:

http://solarfuelshub.org/; "The Joint Center for Artificial Photosynthesis (JCAP) is the nation's largest research program dedicated to the development of an artificial solar-fuel generation technology. Established in 2010 as a U.S. Department of Energy (DOE) Energy innovation Hub, JCAP aims to find a cost-effective method to produce fuels using only sunlight, water and carbon dioxide as inputs";

there are multiple, organized, well-supported efforts underway around the world targeted on the development of technology whereby solar energy, in processes of what might in some cases be thought of as "artificial photosynthesis", can drive the conversion of Carbon Dioxide, in concert with Hydrogen concurrently extracted from the Water, H2O, molecule, into hydrocarbon fuels and other hydrocarbon products.

That Carbon Dioxide can be productively converted into hydrocarbons, into specifically, for one example, substitute natural gas Methane, has, as can be learned via:

CO2 Solution Wins Nobel Prize - in 1912 | Research & Development | News;

been known now, in some apparently few enlightened circles, for more than a century. However, the Sabatier reaction discussed in the above report relies on elemental, molecular Hydrogen to be made available to react with the Carbon Dioxide, while, as seen in:

May 15, 2014, "Real World" CO2-to-Methane Photosynthesis | Research & Development | News; concerning: "United States Patent Application 20140131192 - Ionic Liquid Functionalized Reduced Graphite Oxide / TiO2 Nanocomposite for Conversion of CO2 to CH4 (Methane); May 15, 2014; Inventors: Jean Andino and Tingling Gao, Arizona; (Arizona State University); 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 vaporGovernment 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";

more current CO2-to-Methane development is focused on the use of Water, H2O, as the source of Hydrogen, in integrated processes wherein sunlight powers the concurrent decomposition of Carbon Dioxide into Carbon Monoxide, CO, and of Water, H2O, into Hydrogen, H2, with Oxygen as a byproduct, and, with the CO and H2 being subsequently reacted to form the desired Methane, and more O2 and/or H2O.

As in the above "United States Patent Application 20140131192", and in our reports of:

USDOE Sunlight Converts CO2 into Methane | Research & Development | News; 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"; and:

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";

more recent solar-powered CO2-to-Methane development efforts in the United States are also focused on the discovery and refinement of catalysts to leverage the solar light energy being supplied to the reaction, to make that reaction more effective and the light-driven conversion of CO2 and H2O to Methane more efficient.

And, as seen in our report of:

Korea Improves Solar CO2 to Methane Catalysis | Research & Development | News; concerning: "United States Patent Application 20130192975 - Method of Manufacturing a Porous Gallium (III) Oxide Photocatalyst for Preparation of Hydrocarbons; 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; 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. 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";

similar artificial photosynthesis catalysts, which, when illuminated by sunlight, drive the conversion of Carbon Dioxide and Water into substitute natural gas Methane, are also being developed virtually around the world.

Herein, and we regret what might seem the repetition, we learn that independent technical experts in the employ of our United States Government recently validated the above "United States Patent Application 20130192975", confirming that it is, in fact, real and practicable technology for the solar-powered concurrent conversion of Carbon Dioxide and Water into substitute natural gas Methane; via issuance and allowance of, as excerpted from the initial link in this dispatch:

"United States Patent 8,716,171 - Method of Manufacturing a Porous Gallium (III) Oxide Photocatalyst for Preparation of Hydrocarbons

Patent US8716171 - Method of manufacturing a porous gallium (III) oxide photocatalyst for ... - Google Patents

Method of manufacturing a porous gallium (III) oxide photocatalyst for preparation of hydrocarbons - Korea Advanced Instititut

Date: May 6, 2014

Inventors: Jeung-Ku Kang, et. al., Korea

Assignee: Korea Advanced Instititute of Science and Technology, Daejon, KR

Abstract: The present invention relates to preparation of porous gallium (III) oxide [Ga2O3] photocatalyst for production of hydrocarbons 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 photocatalyst for production of hydrocarbons, manufactured by the foregoing method.

(Don't be distracted by the notation "gallium (III) oxide". The "(III)" is just, as can be learned via: 

Oxidation state - Wikipedia, the free encyclopedia;

 an expression of how many of its electrons Gallium is sharing with other components in a compound.  Gallium(III) compounds are most common, as other references attest. Gallium(II) compounds are known, but less common, and Gallium(I) are only in theory possible.

And, as can be learned via:

China Extracts High-purity, High-tech Metal from Coal Ash | Research & Development | News; concerning: "United States Patent 8,728,296 - Method of Extracting Gallium from Fly Ash; 2014; Inventors: Dazhao Gu, et. al., China; Assignee: China Shenhua Energy Company Limited, Beijing";

Gallium can be, and in fact in China is being, extracted on a commercial, industrial basis from Coal Ash. We could pretty easily get all we might need.)

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. 

The method ... wherein 5 to 10 ml of at least one base selected from ammonium hydroxide (NH4OH), sodium hydroxide (NaOH) and potassium hydroxide (KOH) and 100 to 300 mg of at least one surfactant (as specified) are added to 100 ml of any one solvent selected from water, ethanol and methanol; and the mixture is agitated at 100 to 500 rpm for 30 minutes to 1 hour to form the micelles.

(Although "water", as above, would be the simplest "solvent", it would seem, to use, if either "ethanol" or "methanol" would for some reason be preferable, we are obliged to remind you, that, as seen for only one example in: 

USDOE CO2 + Hydrogen = Methanol and Ethanol | Research & Development | News; concerning: "US Patent 7,858,667 - Alcohol Synthesis from CO or CO2; 2010; Assignee: Battelle Memorial Institute, WA (USDOE Pacific Northwest National Laboratory); Abstract: Methods for producing alcohols from CO or CO2 and H2 utilizing a palladium-zinc (Pd--Zn) on alumina catalyst are described. Methods of synthesizing alcohols over various catalysts in microchannels are also described. Ethanol, higher alcohols, and other C2+ oxygenates can be produced utilizingRh--Mn (Rhodium and Manganese) or a Fisher-Tropsch catalyst. Claims: A method of synthesizing alcohols from CO or CO2 comprising: flowing a reactant gas mixture comprising H2 and CO or CO2 into contact with a catalyst; wherein the catalyst comprises a Pd--Zn alloy dispersed on alumina; and forming an alcohol or alcohols. The method ... wherein the alcohol or alcohols formed in the step of forming an alcohol or alcohols consists essentially of methanol (and, a) A method of synthesizing ethanol or higher alcohols from CO2 comprising: flowing a reactant gas mixture comprising CO2 and H2 into contact with a catalyst; wherein the catalyst comprises: (a) Pd--Zn alloy dispersed on alumina and (b) a Fischer-Tropsch catalyst; and forming ethanol or higher alcohols";

we can synthesize either of them, as well, from Carbon Dioxide.

And, don't be flummoxed by the term "micelles". It just means microscopic "clumps", as it were, of atoms or molecules that automatically cling together, without forming chemical bonds, because of varying electrical charges. They form herein on their own, based on the components of the composition, and they aren't some exotic structure we have to somehow fabricate. For more than you likely want to know, see:

http://www.whatischemistry.unina.it/en/micella.html.)

The method ... wherein the solution containing the gallium precursor comprises a solution prepared by adding 0.5 to 1.5 g of gallium nitrate hydrate (Ga(NO3)3 x H2O) as the gallium precursor to 100 ml of any one solvent selected from water, ethanol and methanol (and processing as further described).

A porous gallium (III) oxide photocatalyst for production of hydrocarbons ... .

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. 

Artificial photo-synthesis technologies that use a photocatalyst to produce useful fuel from carbon dioxide and/or conversion of carbon dioxide to the same are now a global issue.

Such a method of preparing a useful fuel using carbon dioxide and/or converting carbon dioxide to the same substantially utilizes only water and solar light, therefore, may be the most eco-friendly and sustainable technique.

The fuel produced by the foregoing method may include hydrocarbons having 1 to 4 carbon atoms, preferably, aliphatic hydrocarbons having 1 to 4 carbon atoms, and more preferably, methane. 

Methane ... is a main component of natural gas ... . 

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.

Accordingly, the present invention relates to a method of manufacturing a porous gallium (III) oxide photocatalyst with novel structure and form, and a method for production of hydrocarbons, preferably, aliphatic hydrocarbons having 1 to 4 carbon atoms, and more preferably, methane from CO2 or for conversion of CO2 to any of the foregoing hydrocarbons or methane by using the aforesaid porous gallium (III) oxide photocatalyst.

(The) porous GaO3 photocatalyst according to the present invention may have advantages of simple manufacturing process and possibility of mass production. In addition, stable photocatalytic characteristics may be successfully attained on the basis of other preferable features, i.e., a large specific surface area, excellent chemical and thermal properties, stable recycling features, and the like.

Further, because of high CO2 adsorption and reduction potential, the inventive photocatalyst may be possibly used to produce clean fuels such as methane and/or methanol, from CO2 and water."

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We've many times documented that, as immediately above, fuel alcohol "methanol" can, as well, be synthesized from "CO2 and water"; and, we will, without doubt, be discussing those potentials again in the near future. However, it is substitute natural gas Methane that is specified throughout the full disclosure of our subject, "United States Patent 8,716,171 - Method of Manufacturing a Porous Gallium (III) Oxide Photocatalyst for Preparation of Hydrocarbons", to be the main and primary product of using Sunlight to drive the reaction between Carbon Dioxide and Water over the specified and described "Photocatalyst".

And, we again remind you, that, as has been known since before WWII, but as is being reaffirmed more lately in some ominous quarters, as in our report of:

Saudia Arabia CO2 + Methane = Hydrocarbons + Syngas | Research & Development | News; concerning: "United States Patent 7,355,088 - Process for Producing Benzene, Ethylene and Synthesis Gas; 2008; Inventors: Agaddin Mamedov, et. al., Saudi Arabia; Assignee: Saudi Basic Industries Corporation, Riyadh; Abstract: Process for producing benzene, ethylene and synthesis gas, comprising the steps of: i) introducing a starting gas flow comprising methane and carbon dioxide into a reactor; ii) oxidizing the methane in the reactor at certain reactor conditions optionally using a first catalytic material and/or and additional oxidant; and:iii) removing a product gas flow comprising benzene, ethylene and synthesis gas from the reactor";

once we have the Methane, as synthesized, via the processes and with the photocatalyst disclosed herein by "United States Patent 8,716,171", from Carbon Dioxide, we can then react that CO2-based Methane, in what are known as "reforming" reactions, with even more Carbon Dioxide, as recovered from whatever handy source, and thereby generate even more hydrocarbons, and "synthesis gas", a blend of Carbon Monoxide and Hydrogen, which can then be chemically, catalytically condensed via long-known processes, such as the now nearly-ancient and almost-generic "Fischer-Tropsch" synthesis, into a nearly full range of gaseous and liquid hydrocarbon fuels.

Once again, it is demonstrated:

Carbon Dioxide - - as it is co-produced in only a small way, relative to a number of processes that are all-natural, un-taxable and non-political, 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 - - is a valuable raw material resource. 

We can collect Carbon Dioxide from whatever source most convenient to us, and, then, in a process driven by simple and freely-available sunlight, we can convert that Carbon Dioxide, along with Hydrogen concurrently extracted from the Water molecule, into substitute, fracking- free, natural gas Methane.


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