United States Patent Application: 0130122381
West Virginia University has invented a "battery" system which can be recharged by solar- or wind-, and we would presume hydro-, generated electricity; and, which battery, upon discharge, splits Carbon Dioxide and Water into Oxygen, and, into a blend of Carbon Monoxide and Hydrogen, that is, into a hydrocarbon synthesis gas suitable for the catalytic synthesis of hydrocarbon fuels and chemicals.
By way of background, we remind you of a few of our previous reports, which, absent the prior art reference list of a full, allowed and issued US Patent, we perceive as presenting the development of conceptually similar processes, as in, for example:
West Virginia Coal Association | USDOE Hydrocarbon Syngas from CO2 and H2O | Research & Development; concerning: "United States Patent 4,313,925 - Thermochemical Cyclic System for Decomposing H2O and/or CO2 by Means of Cerium-Titanium-Sodium-Oxygen Compounds; 1982; Inventor: Carlos Bamberger, Oak Ridge, TN; Assignee: The USA as Represented by the USDOE; Abstract: A thermochemical closed cyclic process for the decomposition of water and/or carbon dioxide to hydrogen and/or carbon monoxide";
and, which "cyclic process", based, as the full disclosure reveals, on metal oxide chemistry, led to the evolution of, as seen for one example in our report of:
West Virginia Coal Association | More USDOE CO2 "Syntrolysis" | Research & Development; concerning:
"Co-Electrolysis of Steam and Carbon Dioxide for Production of Syngas; Fifth International Fuel Cell Science, Engineering and Technology Conference; July, 2007; J.E. O'Brien, C.M. Stoots, et. al.; Idaho National Laboratory, USDOE; and Ceramatec, Inc., Utah; Abstract: An experimental study has been completed to assess the performance of single-oxide electrolysis cells ... simultaneously electrolyzing steam and carbon dioxide for the direct production of syngas. ... Syngas, a mixture of hydrogen and carbon monoxide, can be used for the production of synthetic liquid fuels via Fischer-Tropsch processes";
what is in some cases called "syntrolysis" technology by our USDOE and their contractors, wherein, in metal oxide, or "single oxide electrolysis cells", sometimes described as fuel cells operated in reverse, Steam, H2O, and Carbon Dioxide, CO2, are electrolyzed at elevated temperatures and converted into a blend of Carbon Monoxide and Hydrogen, or "Syngas", suitable, with apologies for the repetition, "for the production of synthetic liquid fuels via Fischer-Tropsch processes".
The USDOE's and their contractor's, Ceramatec's, efforts no doubt contributed to the development of, as seen in:
West Virginia Coal Association | Utah 2011 CO2 + H2O = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; 2011; Inventors: Joseph Hartvigsen, et. al., Utah; Assignee: Ceramatec, Inc., Salt Lake City; Abstract: A method is provided for synthesizing synthesis gas from carbon dioxide obtained from atmospheric air or other available carbon dioxide source and water using a sodium-conducting electrochemical cell. Synthesis gas is also produced by the coelectrolysis of carbon dioxide and steam in a solid oxide fuel cell or solid oxide electrolytic cell. The synthesis gas produced may then be further processed and eventually converted into a liquid fuel suitable for transportation or other applications";
a formal design for just such a "solid oxide electrolytic cell" for the production, from CO2 and H2O, of synthesis gas; which syngas is suitable for conversion "into a liquid fuel suitable for transportation".
And, as we further reported, via:
West Virginia Coal Association | WVU September 2012 CO2 into Hydrocarbon Syngas | Research & Development; concerning: "United States Patent Application 20120228150 - CO2 Decomposition Via Oxygen Deficient Ferrite Electrodes Using Solid Oxide Electrolyser Cell; 2012; Inventors: Bruce S. Kang, Huang Guo and Gulfam Iqbal, Morgantown, WV; (Presumed eventual Assignee of Rights: West Virginia University); Abstract: Oxygen Deficient Ferrites (ODF) electrodes integrated with Yttria Stabilized Zirconia (YSZ) electrolyte, electrochemically decompose carbon dioxide (CO2) into carbon (C)/carbon monoxide (CO) and oxygen (O2) in a continuous process. The ODF electrodes can be kept active by applying a small potential bias across the electrodes. CO2 and water (H2O) can also be electrolyzed simultaneously to produce syngas (H2+CO) and O2 continuously that can be fed back to the oxy-fuel combustion. With this approach, CO2 can be transformed into a valuable fuel source allowing CO2 neutral use of the hydrocarbon fuels.Claims: A method to decompose CO2 into C/CO and O2 using Oxygen Deficient Ferrites ... electrodes integrated with solid oxide electrolyser cell. Background and Field: The present invention relates to the decomposition of carbon dioxide into carbon/carbon monoxide and oxygen via oxygen deficient ferrite (ODF) electrodes in a continuous process using solid oxide electrolyser cell (SOEC). Another application is the co-electrolysis of CO2 and water to produce syngas for fuel or further processing. A preferable approach would be to decompose CO2 into C/CO and oxygen, or co-electrolysis with H2O to generate syngas (H2+CO) and oxygen (O2). ... Syngas can ... be further processed into synthetic liquid fuel (synfuel) through the Fischer-Tropsch process";
what we perceive to be similar, closely-related Carbon Dioxide-to-Syngas, CO2 and H2O co-electrolysis technology, has lately been developed by Professor Bruce S. Kang, and colleagues, at West Virginia University.
And, herein we learn that Dr. Kang and his WVU colleagues have continued to develop and refine their version of Carbon Dioxide and Water co-electrolysis technology for the production of syngas, with both more effective electrode materials and a process design that will allow inclusion of other, what might be thought of as, "greenhouse gases".
As seen, with comment inserted and appended, in excerpts from the initial link in this dispatch to:
"United States Patent Application 20130122381 - High Temperature Rechargeable Battery For Greenhouse Gas Decomposition And Oxygen Generation
Date: May 16, 2013
Inventors: Bruce S. Kang and Huang Guo, Morgantown, WV
(No official "Assignee of Rights" is currently published for this patent application. But, as can be learned via:
http://www.mae.cemr.wvu.edu/
http://www2.cemr.wvu.edu/~
Dr. Kang is a Professor of Mechanical and Aerospace Engineering on the faculty of West Virginia University's Benjamin M. Statler College of Engineering and Mineral Resources; and, one "H. Guo" is one of his current PhD. students.)
Abstract: This invention shows a high temperature rechargeable battery system for energy storage, oxygen generation, and decomposition of oxygen-containing gases (e.g. CO2/H2O, NOx, SOx, in particular greenhouse gas (GHG)) ... . The adoption of cost effective materials other than Lithium is significant for scaled-up applications and represents an entirely new approach. With carbon capture and sequestration becoming a key element in worldwide efforts to control/minimize CO2 emission, it can be anticipated that large amount of CO2 will become available for use as feedstock for innovative conversions into synthetic fuels. This invention shows a high temperature rechargeable battery system for decomposition of oxygen containing gases (in particular greenhouse gas (GHG)), oxygen generation, and energy storage ... in a rechargeable Li/Ti/Mg-CO2 battery architecture. Different from traditional Lithium ion conducting electrolyte, the invention has a higher ionic oxygen conducting electrolyte, which can work efficiently at higher temperature without sacrificing safety. During battery discharge, GHG such as CO2/H2O, NOx and SOx can be decomposed into syngas (CO+H2) or solid carbon. Whereas, solar, wind or other renewable energy can be used to charge the battery and generate oxygen. The energy consumption for GHG decomposition is self-sustainable with the integrated system and the byproducts (i.e. solid carbon, syngas (CO+H2), O2) have good market values. The adoption of cost effective materials other than Lithium is significant for scaled-up applications and represents an entirely new approach ... (in) battery architecture.
(Reasonable understanding of what is being described, for those of us not that well educated in the technicalities, can best be achieved by referring to schematics of the device and process, as in the full application document accessible via:
Further, note that other major components of "greenhouse gas", i.e., "NOx and SOx" can be processed, as well, for the electrolytic evolution of products; much as in, and in a way similar to, the process disclosed in our report of:
West Virginia Coal Association | New Jersey Converts CO2 and Nitrogen Oxides into Fertilizer | Research & Development; concerning: "United States Patent 8,524,066 - Electrochemical Production of Urea from NOx and Carbon Dioxide; September 3, 2013; Inventors: Narayanappa Sivasankar, et. al., NJ; Assignee: Liquid Light Inc., NJ; Abstract: Methods and systems for electrochemical production of urea are disclosed. A method may include, but is not limited to, steps (A) to (B). Step (A) may introduce carbon dioxide and NOx to a solution of an electrolyte and a heterocyclic catalyst in an electrochemical cell. The divided electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode may reduce the carbon dioxide and the NOx into a first sub-product and a second sub-product, respectively. Step (B) may combine the first sub-product and the second sub-product to produce urea".
Additional understanding might be achieved by an explanation of the process provided in:
Carbon Dioxide Decomposition and Oxygen Generation Via SOEC; concerning: "'Carbon Dioxide Decomposition and Oxygen Generation Via SOEC';
- Huang Guo, Bruce Kang and Ayyakkannu Manivannan;
Oxygen-Deficient Ferrite (ODF) or nickelate-based materials are mixed with YSZ powder via Mechano-Chemical Bonding (MCB) process. The Solid Oxide Electrolyzer Cell (SOEC) with ODF/YSZ or nickelate/YSZ electrodes and YSZ electrolyte is utilized to decompose carbon dioxide (CO2) into solid carbon (C) or carbon monoxide (CO) and generate oxygen (O2) in a continuous process. ... In our preliminary tests, CO or solid carbon at cathode side and O2 at anode side were detected, when CO2 was fed to the cathode side and a small potential bias applied across the electrode. Depending on the applied potential, the system is capable of decomposing CO2 into CO or C. ... An energy assessment shows that the net energy input in this process is smaller compared to CCS (carbon capture and sequestration)".
Make special note, as in the above, that, significantly, such Carbon Dioxide utilization processes require less "net energy input" than specious alternatives like geologic "sequestration".)
Claims: A high temperature rechargeable battery system for decomposition of oxygen-containing gases such as NOx, SO2, H2O, CO2, in particular greenhouse gas (GHG), oxygen generation and energy storage is invented by introducing an oxygen-deficient ferrites (MxFe3xO4. M represents a bivalent metal ion, in particular Fe(II), Cu(II), Co(II), Mn(II) or Ni(II)) and/or La2NiO4-based materials into rechargeable Li/Ti/Mg-CO2 batteries. During discharge of the battery, oxygen-containing gases like GHG can be decomposed into syngas (CO+H2) or solid carbon while renewable energy such as solar or wind energy can be used to charge the battery and generate pure oxygen.
Background and Field: The present invention relates to the high temperature rechargeable battery system using oxygen ion conducting electrolyte which could be capable of utilizing renewable energy sources such as solar or wind power for energy storage and efficiently converting GHG, into useable syngas, solid carbon and oxygen. The byproducts which have good market values can be used as fuel or for further processing. The usage of cheaper electrode materials (i.e. Ti/TiO2, Mg/MgO) other than Lithium can significantly reduce material cost of the scaled-up battery system and work efficiently at higher temperature without sacrificing safety.
Current approaches for the reduction of CO2 emission from large-scale fossil fuel facilities focus on carbon capture and storage (CCS) ... . Capture of CO2 for recycling, which is faced with several challenges as it is still in its infancy and very costly, can be achieved by absorption processes employing amines or carbonates as absorbents. The regeneration requires heating of the absorbent. This process consumes a significant portion (about.25%) of the power plant energy output. Thus, energy consumption of the process must be reduced in order to fully realize the utility of CO2 recycling.
Moreover, the captured CO2 is to be sequestrated to a permanent place which is another energy-consuming process and eventually, available/suitable sites for CCS sequestration will be limited.
Other preferable technology currently being examined is using captured, anthropogenically produced CO2 for the synthesis of syngas through the use of catalysts or solid oxide electrolyte cells ... .
Syngas can ... be further processed into hydrocarbon and carbonaceous fuels, such as Diesel, Methanol, Ammonia, and so on.
Recently, a new CO2-rich gas-utilizing battery has been developed ... . This Li--O2/CO2 battery utilizes a mixed gas of O2 and CO2, and has nearly three times of discharge capacity than that of a standard Li-O2 battery. The disadvantage of it is that this kind of new battery is non-rechargeable due to the difficulty of electrochemical decomposition of Li2CO3 in the cathode.
Summary: The present invention utilizes a central module composed of a rechargeable Li/Ti/Mg battery consisting of an ODF/La2NiO4-based cathode, a carbon-free ion conducting electrolyte ... and a Li/Ti/Mg anode.
Renewable energy sources such as solar or wind energy can be utilized to charge the battery, where the Li/Ti/Mg oxides can be reduced to metallic Li/Ti/Mg at the anode, producing pure oxygen at the cathode as a side product.
In the battery discharge mode, at elevated temperatures, CO2 or a combination of CO2/H2O can be fed into the cathode side, generating syngas (CO + H2) and/or solid carbon while simultaneously generating electricity.
The energy consumption for CO2 decomposition is self-sustainable with the integrated system, i.e. using renewable energy such as solar or wind energy, and the byproducts (i.e. ... syngas (CO + H2), O2) have good market values.
Instead of the Lithium ion conducting electrolyte in traditional Li ion battery, the oxygen ion conducting electrolytes has higher ionic conductivity ... and eliminates the safety problem associated with using organic/flammable electrolytes without causing cathode clogging. The elevated operating temperature enhances its high ionic oxygen conductivity and battery efficiency as well. The adoption of cost effective anode materials (i.e. Ti/TiO2, Mg/MgO) other than Lithium is significant for scaled-up applications and represents an entirely new approach."
--------------------------
And, while we consider this West Virginia University innovation, this "entirely new approach", for the direct, productive use of Carbon Dioxide in the synthesis, via intermediate production of synthesis gas, of hydrocarbons, we remind you of other West Virginia University innovations for the indirect, via botanical and organic intermediates, productive use of Carbon Dioxide, as seen for one example in our report of:
West Virginia Coal Association | WVU Coal and Carbon-recycling Renewables into Crude Oil | Research & Development; concerning, primarily: "United States Patent 8,597,382 - Rubber Material In Coal Liquefaction; 2013; Inventor: Alfred H. Stiller, Morgantown, WV; Assignee: West Virginia University; Abstract: The present disclosure provides methods and systems for coal liquefaction using a rubber material. ... The method ... wherein the rubber material is from a rubber tire. ... The method ... wherein the coal is selected from one or more of a sub-bituminous coal, a bituminous coal, a lignite coal, and an anthracite coal (and, the) de-ashed coal extract may be added to a pipeline of petroleum crude for delivery to a petroleum refinery";and which also contained links to our reports concerning: "United States Patent 8,449,632 - Sewage Material in Coal Liquefaction; May 28, 2013; Inventor: Alfred H. Stiller, Morgantown, WV; Assignee: West Virginia University; Abstract: The present disclosure provides methods and systems for coal liquefaction using a sewage material. ... The de-ashed coal extract may be added to a pipeline of petroleum crude for delivery to a petroleum refinery"; and: "United States Patent 8,465,561 - Hydrogenated Vegetable Oil in Coal Liquefaction; June 18, 2013; Inventors: Alfred H. Stiller and Elliot B. Kennel, Morgantown, WV; Assignee: West Virginia University; Abstract: The present disclosure provides methods and systems for coal liquefaction using a hydrogenated vegetable oil";
wherein naturally CO2-recycling materials like "vegetable oil" and "sewage material" can be combined with Coal in the production of synthetic hydrocarbons.
As an additional and repetitive note for emphasis, pure Oxygen is co-produced by the process of our subject, "United States Patent Application 20130122381 - High Temperature Rechargeable Battery For Greenhouse Gas Decomposition And Oxygen Generation"; and, such Oxygen, as indicated to a certain extent in the full Disclosure, would have value as an industrial commodity, which value would help to offset the costs of producing such things as, ultimately, "synthetic fuels", from Water and Carbon Dioxide.
There is, obviously, a lot of work going on at West Virginia University that could have magnificent impacts on our national security - - through innovations that could provide for completely domestic sources of our hydrocarbon fuel needs, thus freeing us from economic and military bondage to the alien nations of OPEC, while establishing a new United States industrial infrastructure that, while providing many new jobs in the mining, chemical processing and agricultural industries, contributed, through the direct and indirect consumption and use of "greenhouse gases", to the improvement of our natural environment.
If the past really is a prognosticator of the future, then we suspect all of that still won't be enough to motivate our Mountain State journalistic community to pull their noses out of the gas pipe, get off their dead cans and make certain the Mountain State general public gets to read, or hear, all about it.
Which, of course, is a shame. It's far past time all of us were treated to some genuinely good, and truly significant, news.