United States Patent Application: 0130032470
We remind you that we have made previous report of the fact, that, as seen in:
West Virginia Coal Association | Pittsburgh USDOE Converts CO2 to Methane & Methanol | Research & Development; concerning: "'Visible Light Photoreduction of CO2'; 2009; National Energy Technology Laboratory, USDOE, Pittsburgh, PA; Abstract: A series of ... Titanium Dioxide (catalysts) have been synthesized, characterized, and tested for the photocatalytic reduction of CO2 in the presence of H2O. Our results show that these ... materials are capable of catalyzing the photoreduction of CO2 using visible light illumination ... . The ... analysis shows that the primary reaction product is CH4"; and:
West Virginia Coal Association | Pittsburgh USDOE Photo-Converts Methane to Methanol | Research & Development; concerning: "United States Patent 5,720,858 - The Photocatalytic Conversion of Methane; 1998; Inventor: Richard Noceti, et. al., Pittsburgh, PA; Assignee: The United States of America; The United States Government has rights to this invention pursuant to employee/employer relationship of the inventors to the U.S. Department of Energy at the Pittsburgh Energy Technology Center. Abstract: A method for converting methane to methanol is provided comprising subjecting the methane to visible light in the presence of a catalyst and an electron transfer agent";
our own US Government has been at work over the past decade and a half confirming that plain old sunlight, in properly catalyzed reactions, has the power to, first, convert Carbon Dioxide and H2O into Methane, and, then, to convert that Methane into the fuel alcohol, Methanol.
Much of that, as seen in our reports 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, et. al.; The Pennsylvania State University; 2009; Efficient solar conversion of carbon dioxide and water vapor to methane ... is achieved using nitrogen-doped titania nanotube arrays ... . All experiments are conducted in outdoor sunlight at University Park, PA"; and:
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:
West Virginia Coal Association | USDOE Hires Penn State to Enable CO2 Recycling | Research & Development; concerning: "United States Patent Application 20100187172 - Highly Ordered Titania Nanotube Arrays;
(HIGHLY-ORDERED TITANIA NANOTUBE ARRAYS - THE PENN STATE RESEARCH FOUNDATION
Patent US20100187172 - Highly-ordered titania nanotube arrays - Google Patents)
2010; Inventors: Maggie Paulose, ... Craig Grimes, et. al.; Assignee: The Penn State Research Foundation; Abstract: Fabrication of self-aligned closed packed titania nanotube arrays in excess of 10 .mu.m in length and aspect ratio .apprxeq.10,000 by potentiostatic anodization of titanium is disclosed. Conditions for achieving complete anodization and absolute tailorability of Titanium foil samples resulting in a self-standing mechanically robust titania membrane in excess of 1000 .mu.m are also disclosed. Government Interests: This invention was developed with government support under Grant No. DE-FG02-06ER15772, awarded by The Department of Energy, and under Grant No. CTS-0518269 awarded by the National Science Foundation. The government has certain rights in this invention";
has been more lately confirmed, and the technology advanced, by scientists at Penn State University, also working in concert with the United State Department of Energy.
And, herein, we learn that scientists on the other side of our continent have advanced such processes for the use of such "titania nanotube"s in a way that more directly harnesses the energy of sunlight to drive the conversion of Water and that increasingly-precious raw material resource, Carbon Dioxide, into Methanol.
As seen in excerpts from the initial link in this dispatch to the recent publication of:
"United States Patent Application 20130032470 - Systems Including Nanotubular Arrays for Converting Carbon Dioxide to an Organic Compound
SYSTEMS INCLUDING NANOTUBULAR ARRAYS FOR CONVERTING CARBON DIOXIDE TO AN ORGANIC COMPOUND - Reno
Date: February 7, 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.Claims: A system for converting carbon dioxide to an organic compound, the system comprising: an anode including an array of nanotubes; a cathode including an electrically conductive material, the cathode cooperates with the anode to receive electrons from the anode; an electrically conductive fluid, the anode and cathode being at least partially immersed in the electrically conductive fluid; a light source that irradiates at least the anode; 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 via contact with the anode, cathode, or both.
The system ... wherein the nanotubes are titania nanotubes (and) the titania nanotubes are carbon modified.
The system ... wherein the nanotubes are titania nanotubes including nanoparticles of an electron mediator dispersed on a surface of the nanotubes (and) wherein the electron mediator is palladium.
The system ... wherein the electrically conductive fluid is a dilute sulfuric acid solution ... .
The system ... wherein the light source irradiates visible light.
The system ... wherein the carbon dioxide is converted to methanol.
(So, with the "titania nanotubes", which, as seen in our introductory references, Penn State University knows how to make, and, with nothing but "visible light" to power the process, and using only common as dirt "sulfuric acid solution" as the only other reagent/reactant needed, we can convert CO2 into "methanol".
And, here seems a good place to remind you, that, as seen for one example in our report of:
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. ... This invention provides a process for producing methanol by the substantially thermoneutral reaction of steam with coal; and:
"United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation. ... The conversion of methanol to gasoline ... is described";
Methanol, regardless of which of our precious natural resources, whether Coal or, as herein, Carbon Dioxide, we make it from, can be directly and efficiently converted into some of the stuff, "gasoline", we seem so willing fight foreign desert wars for the privilege of paying international extortionists through the nose to keep ourselves supplied with.
Further, this might be a good place to point out that this seems a Carbon Dioxide recycling process more akin in general concept to that now being operated on an industrial basis in the nation of Iceland, by the company Carbon Recycling International, as documented for only one example in our report of:
West Virginia Coal Association | Sweden Makes Public Report of CO2 to Motor Fuel Recycling | Research & Development; concerning the Swedish news article: "'Iceland As A Green Saudi Arabia'; March 12, 2013; Recently, they shipped the first load to oil company Argos in Holland, for low level blending in gasoline. Vulcanol is just a name for methanol, regular wood spirit. It is the production method which makes this fuel especially interesting. It is made using renewable electricity, water and captured CO2";where, using a somewhat different reaction technology, they are converting industrial exhaust gas CO2, on a commercial basis, directly into Methanol, without an intermediate synthesis of Methane, as might be suggested by our introductory citations, above, of the report "Visible Light Photoreduction of CO2" and of "United States Patent 5,720,858 - The Photocatalytic Conversion of Methane".)
Background: The present invention relates generally to nanostructure arrays and uses thereof for converting carbon dioxide to an organic compound.
Pumping CO2 from fossil fuel power plants into deep ocean basins is one of the most discussed disposal options (for dealing with supposedly adverse CO2 accumulations).
Another potential option is converting this greenhouse gas into alternate fuels.
For example, CO2 feedstock can be converted into fuels of solid, liquid, or gas phase by chemical, electrolytic, photocatalytic, or photo-electro-catalytic methods. However, reduction of CO2 to fuel form of any phase requires energy, which can make the process unattractive both from an economical standpoint and because the process can create yet more CO2. Similarly, processes that are carried on at high temperatures or pressures can be unattractive.
Electrolytic conversion of CO2 into ... methane, ethane, ethylene, methanol, ethanol, n-propanol, formic acid, and formaldehyde has been widely reported.
(Concerning the above, see, for just a few examples, our reports of:
West Virginia Coal Association | Chicago Recycles CO2 to Methane | Research & Development; concerning: "US Patent 4,609,440 - Electrochemical Synthesis of Methane; 1986; Assignee: Gas Research Institute, Chicago; A method is described for electrochemically reducing carbon dioxide to form methane by electrolyzing an aqueous solution containing carbon dioxide"; and:
West Virginia Coal Association | USDOE 1976 Atmospheric CO2 to Methanol | Research & Development; concerning: "US Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Assignee: The USA as represented by the USDOE; A method ... for synthesizing methanol from the CO2 in air using electric power. The CO2 is absorbed by a solution of KOH to form K2CO3 which is electrolyzed to produce methanol, a liquid hydrocarbon fuel".)
Electrolytic conversion of CO2 to useful products typically suffers from a number of limitations. For example, the reaction ... can be kinetically limited because of the low solubility of CO2 in water. In addition, in aqueous solutions, hydrogen evolution can compete with methanol formation.
It also appears that processes to date for converting CO2 to methanol rely on indirect power sources to supply the necessary energy, rather than using more direct energy sources, such as solar energy.
Summary: In one embodiment, a system is disclosed for converting carbon dioxide to an organic compound. The system 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.
(Again, the "electrically conductive fluid" can be just common sulfuric acid, which is an industrial commodity. The use of it helps to overcome the energy inefficiencies in similar, older CO2 electrolysis designs that relied on Water, H2O, as the primary conductive fluid and Hydrogen donor.)
In another embodiment, the system includes an anode, a cathode, and an electrically conductive material. The anode includes an array of nanotubes, e.g., titania nanotubes. The cathode includes an electrically conductive material and also cooperates with the anode to receive electrons therefrom. The anode and cathode are at least partially immersed in the electrically conductive fluid. The system further includes a light source that irradiates at least the anode, 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 the cathode, anode, or both.
In another embodiment, a method for converting carbon dioxide to an organic compound is disclosed. The method includes irradiating an array of nanotubes at least partially immersed in an electrically conductive fluid. The array of nanotubes includes nanoparticles of an electron mediator, e.g. palladium, that are dispersed on a surface of the nanotubes. The method further includes delivering 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 the irradiated array of nanotubes. In one example, the array is an ordered array of titania nanotubes.
The system further includes a light source, such as a solar light, e.g., the sun, that irradiates the array of nanotubes with light, e.g., visible light.
The system also includes a source of carbon dioxide and an inlet tube for delivering the carbon dioxide to the electrically conductive fluid whereat at least a portion of the carbon dioxide is converted to methanol via contact with an irradiated array of palladium-sensitized titania nanotubes.
In one example, the source of the carbon dioxide is a fossil fuel, e.g., coal, which upon burning or combustion at a plant, for example, releases carbon dioxide as a byproduct."----------------------
We closed our excerpts with the above passage to emphasize the point:
We could, and should, start to view, and treat, the Carbon Dioxide that is co-produced by our essential use of Coal in the generation of abundant, reliable and truly affordable electric power "as a byproduct".
The full disclosure of our subject herein, "United States Patent Application 20130032470 - Systems Including Nanotubular Arrays for Converting Carbon Dioxide to an Organic Compound", indicates that the Carbon Dioxide is to be delivered as a gas, or compressed liquid, to the sulfuric acid electrolytic bath; and, we remind you, that, as seen for two examples in our reports of:
West Virginia Coal Association | WVU March 28, 2013, Economical Harvesting of Flue Gas CO2 | Research & Development; concerning: "United States Patent Application 20130078172 - Layered Solid Sorbents for Carbon Dioxide Capture; 2013; Assignee: West Virginia University Research Corporation, Morgantown; Abstract: A solid sorbent for the capture and the transport of carbon dioxide gas is provided"; and:
West Virginia Coal Association | Renewable Energy Reclaims Coal Power Plant CO2 | Research & Development; concerning: "United States Patent Application 20130152596 - Fossil Fuel-Fired Power Station Having A Removal Apparatus For Carbon Dioxide And Process For Separating Carbon Dioxide From An Offgas From A Fossil Fuel-Fired Power Station; 2013; Assignee: Siemens Aktiengesellschaft, Germany; Abstract: A fossil fuel-fired power station having a removal apparatus for carbon dioxide which is located downstream of a combustion facility and through which an offgas containing carbon dioxide may flow is provided. The removal apparatus comprises an absorption unit and a desorption unit. The desorption unit is connected to a renewable energy source";
we are getting better and better at harvesting Carbon Dioxide from, as the University of Nevada herein specifies, "coal, which upon burning or combustion at a plant, for example, releases carbon dioxide as a byproduct".
Further, we note since it might not be perfectly clear in our excerpts, that, although this is a process that can, and is specified to, be driven by light energy, it is actually electro-chemical energy, with the electric current or potential being generated by a photo-electric process, that is getting the job of chemically reducing the Carbon Dioxide, and forming the Methanol, done.
Quite conceivably, using the same reaction environment specified herein to lower the amount of electric current needed to effect the chemical reduction of CO2, the system could be powered directly by an alternative source of electrical energy, perhaps as generated by wind power. However, we note that we have as well seen reference made, since these photo-electric catalysts can be very sensitive and efficient, to the use of artificial light to drive such CO2-conversion chemical reactions.
In any case:
Carbon Dioxide is a "byproduct", we summarize, of our Coal use, which we can efficiently reclaim, and, as herein confirmed by the University of Nevada, then directly transform, using freely-available environmental energy, "visible light", to drive the process, into the valuable fuel alcohol, Methanol.