United States Patent: 8658311

We first remind you of our recent report:

Panasonic Photosynthesizes More Hydrocarbons from CO2Panasonic Photosynthesizes More Hydrocarbons from CO2 | Research & Develo;

which concerned a couple of recently-validated Carbon Dioxide utilization, "artificial photosynthesis",  technologies developed by Japan's Panasonic Corporation, such as, for one example:

 

"United States Patent 8,709,228 - Method for Reducing Carbon Dioxide; April 29, 2014; Inventors: Masahiro Deguchi, et. al., Japan; Assignee: Panasonic Corporation, Osaka; Abstract: A method for reducing carbon dioxide utilizes a carbon dioxide reduction device including a cathode chamber, an anode chamber (and), a solid electrolyte membrane, a cathode electrode and anode electrode. ... The anode electrode is irradiated with a light having a wavelength of not more than 350 nanometers to reduce the carbon dioxide on the cathode electrode. ... The method ... wherein ... at least one of formic acid, carbon monoxide and hydrocarbon is obtained. It is desirable that this light has a wavelength of not less than 250 nanometers and not more than 325 nanometers".

In that report, we included in our closing comments a separate link to, and excerpts from, a news story we think related to the spirit of the science exemplified by "United States Patent 8,709,228":  

Wyoming U.S. Sen. Enzi backs bill for carbon dioxide capture credits"A Wyoming U.S. senator is one of three legislators sponsoring a bill that would make it easier for companies to attain tax credits for capturing man-made carbon dioxide. Sen. Mike Enzi is co-sponsoring the bill, introduced by Sen. Kent Conrad, D-N.D., in September and co-sponsored by Sen. John “Jay” Rockefeller, D-W.Va.

The bill is aimed at encouraging the capture and use of the greenhouse gas".

Given that West Virginia's US Senator Rockefeller is serving admirably as one of the co-sponsors of legislation that would, if enacted, encourage both "the capture and use" of Carbon Dioxide, we remind you of another of our reports, wherein it's demonstrated that technology for the "use of" CO2 has, in fact, been developed by scientists working in West Virginia, presumably at West Virginia University:

WVU Battery Converts CO2 + H2O into Hydrocarbon Syngas | Research & Development | News; concerning:

"United States Patent Application 20130122381 - High Temperature Rechargeable Battery For Greenhouse  Gas Decomposition And Oxygen Generation; May 16, 2013; Inventors: Bruce S. Kang and Huang Guo, Morgantown, WV; 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)) ... . ... 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. (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".

In that report, we documented and explained how West Virginia University scientists had developed what might be thought of as - -

in a  label used to describe other, similar technology developed, as in other of our reports, by the USDOE and their contractors, as seen for only one brief example in:

More USDOE CO2 "Syntrolysis" | Research & Development | News; 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. Introduction: A research project is underway at the Idaho National Laboratory (INL) to investigate the feasibility of producing syngas by simultaneous electrolytic reduction of steam and carbon dioxide ... . Syngas, a mixture of hydrogen and carbon monoxide, can be used for the production of synthetic liquid fuels via Fischer-Tropsch processes";

- - a "reverse fuel cell", wherein the typical products of hydrocarbon combustion, Carbon Dioxide and H2O being the examples of most interest, could, through the application of electrical energy - - preferably electrical energy generated by environmental source, such as wind or hydro - - be converted back into energetic chemical compounds, such as what is known as hydrocarbon synthesis gas, or "syngas", a blend of Carbon Monoxide and Hydrogen, which syngas can, via known processes like the nearly-ancient Fischer-Tropsch synthesis. be catalytically, chemically condensed into both liquid and gaseous hydrocarbons, like the above "Diesel, Methanol", etc.

And, herein, we learn that, just a few months ago, independent technical experts in the employ of our United States government confirmed the validity and the practicability of "United States Patent Application 20130122381", through their allowance of, as excerpted from the initial link in this dispatch:

"United States Patent 8,658,311- High Temperature Rechargeable Battery for Greenhouse Gas Decomposition and Oxygen Generation

Patent US8658311 - High temperature rechargeable battery for greenhouse gas decomposition and ... - Google Patents

High temperature rechargeable battery for greenhouse gas decomposition and oxygen generation - Kang, Bruce S.

Date: February 25, 2014

Inventors: Bruce S. Kang and Huang Guo, Morgantown, WV

(Note: In our report of "United States Patent Application 20130122381", we speculated that - - since separate references we included in that report confirmed and explained that Bruce S. Kang was employed as a professor by, and Huang Guo was a student and research assistant at, West Virginia University - - WVU would be the "Assignee" of rights to any patent issuing from Application 20130122381. That does not appear to be the case; and, the development of the technology disclosed herein might have been developed by Kang and Guo independently, or, under some sort of special arrangement with WVU.)

Abstract: Instead of CCS (Carbon Capture and Storage) technique, a possible approach to mitigate the greenhouse gas (GHG) emission is to decompose it into useful products. This invention shows a high temperature rechargeable battery system for decomposition of oxygen-containing gases (e.g CO2/H2O, NOx, SOx, in particular GHG), oxygen generation, and energy storage by using ODF/La2NiO4-based materials in Li/Ti/Mg--CO2 battery architecture. Different from ionic Lithium conducting electrolyte, the invention has a higher ionic oxygen conducting electrolyte to work efficiently at higher temperature without sacrificing safety. During battery discharge, GHG can be decomposed into syngas (CO+H2) or solid carbon, while renewable energy (e.g. solar/wind power) could be used to charge the battery and generate oxygen. The energy consumption for GHG decomposition is self-sustainable and the byproducts (i.e. carbon/syngas and oxygen) 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.

(As interesting as the above might sound as a way of collecting, and then utilizing, Carbon Dioxide, as retrieved from whatever handy source, a review of Dr. Kang's research interests and publications, as accessible via: 

Welcome to Dr. Kang's Home Page;

suggests that Dr's Kang and Guo might have some specific, and perhaps intriguing, applications in mind for their CO2-recycling invention, which invention, again, is at least conceptually related to the USDOE's solid oxide reverse fuel cell. And, Kang's and Guo's intent might be congruent with one of the USDOE's proposed uses for their related technology, as expressed in our report of, with apologies for the lengthy excerpts:

USDOE Reforms Coal Syngas CO2 for Hydrocarbon Synthesis | Research & Development | News; concerning:

"United States Patent 8,366,902 - Methods and Systems for Producing Syngas; 2013; Assignee: Battelle Energy Alliance, LLC, Idaho Falls; Abstract: Methods and systems are provided for producing syngas utilizing heat from thermochemical conversion of a carbonaceous fuel to support decomposition of at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells. Simultaneous decomposition of carbon dioxide and water or steam by one or more solid-oxide electrolysis cells may be employed to produce hydrogen and carbon monoxide. A portion of oxygen produced from at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells is fed at a controlled flow rate in a gasifier or combustor to oxidize the carbonaceous fuel to control the carbon dioxide to carbon monoxide ratio produced. Government Interests: This invention was made with government support under Contract Number DE-AC07-05ID14517 awarded by the United States Department of Energy. The government has certain rights in the invention. The method ... wherein producing heat and a mixed gas comprising carbon dioxide, carbon monoxide, water and hydrogen by gasifying a carbonaceous fuel comprises gasifying the carbonaceous fuel in the presence of a portion of the oxygen formed by electrolyzing carbon dioxide and steam to control a ratio of carbon monoxide and hydrogen produced by electrolyzing the carbon dioxide and the steam. Embodiments of the present invention relate, generally, to the production of syngas and, more particularly, to methods and systems for producing syngas from a carbonaceous fuel, such as biomass (and) coal ... by utilizing the heat from thermochemical conversion of the carbonaceous fuel to support electrolysis of steam and/or co-electrolysis of steam and carbon dioxide in one or more solid-oxide electrolysis cells. ... A known process for conversion of these energy resources to cleaner fuels includes synthetic fuels, often referred to as "synfuels," which are made from synthesis gas, often referred to as "syngas." Syngas includes a mixture of varying amounts of carbon monoxide (CO) and hydrogen (H2) that may be converted to form hydrogen, synfuels, methanol or chemicals. Production of synfuels from syngas may be performed using a variety of processes including a Fischer-Tropsch process to convert the carbon monoxide and hydrogen into liquid hydrocarbons.  The synfuels produced using the Fischer-Tropsch process may include high purity, low sulfur, fuels, often referred to as "Fischer-Tropsch liquids," which have fewer pollutants than naturally occurring fuels or fuels processed from naturally occurring oil deposits.  Another approach is to convert syngas into methanol, which may be converted to gasoline, olefins, or aromatics. Syngas may be converted to methanol using a copper or zinc catalyst such as a modified ZSM-5 catalyst. Various embodiments of the present invention include methods and systems for producing hydrogen or syngas by employing thermochemical conversion of a carbonaceous fuel to produce heat to support one or more solid-oxide electrolysis cells. By utilizing heat produced during the thermochemical conversion of the carbonaceous fuel, an external heat source is not needed in the methods and systems. In accordance with one embodiment of the present invention, a method is provided for producing syngas. The method includes thermochemically converting a carbonaceous fuel to produce a heated mixed gas. The heated mixed gas may include water, hydrogen, carbon monoxide and carbon dioxide. The term "high temperature electrolysis process" is used to refer to the electrolytic decomposition of water into hydrogen and oxygen at a temperature above 500 C, while the term "co-electrolysis process" is used to refer to the simultaneous electrolytic decomposition of water into hydrogen and oxygen and carbon dioxide into carbon monoxide and oxygen. The term "carbonaceous fuel," as used herein, means and includes (by) way of example only ... a biomass source composed primarily of vegetative matter, such as corn stover, wheat straw, barley straw, tree bark, wood waste, cellulose, bagasse, municipal wastes and combinations thereof. Additionally, the carbonaceous fuel may include a fossil fuel (and) the fossil fuel may be coal. The syngas produced from the carbonaceous fuel may be converted to synfuel using a process known in the art such as, for example, a Fischer-Tropsch process".

Again, we regret the long excerpts, but they help to explain how our subject, "United States Patent 8,658,311- High Temperature Rechargeable Battery for Greenhouse Gas Decomposition and Oxygen Generation", might be put to very good work. That is, in a process for the partial oxidation or partial combustion, the gasification, of Coal and Biomass, to form a syngas blend of Carbon Monoxide and Hydrogen suitable for "synfuel" production, perhaps via "a Fischer-Tropsch process", wherein heat arising from the gasification can be used directly or indirectly to drive the "Battery", or reverse fuel cell, and to break down any byproduct CO2 and H2O in the product syngas into more of the desired Carbon Monoxide and Hydrogen. Elemental,  molecular Oxygen is a byproduct of the CO2/H2O reforming process of our subject, "United States Patent 8,658,311"; and, that byproduct Oxygen can be reclaimed and cycled back to the gasification process, to support the partial oxidation of the Biomass and Coal.)

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 (MxFe3-xO4-5, 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, wherein 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

(Note the potential for reducing oxides of Nitrogen and Sulfur, as well. As valuable as such applications might be, with the potential for generating other products, such as elemental Sulfur, for instance, we prefer to focus on the CO2-recycling, synthetic fuel aspects; as, apparently, do the inventors. The above, by the way, is the one and only claim of this invention.)

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 ... 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. ... 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 (SOEC). 

Syngas can be utilized as substitute fuel gas for power plants or existing industrial boilers. Syngas can also be further processed into hydrocarbon and carbonaceous fuels, such as Diesel, Methanol, Ammonia, and so on.

These techniques, in order to be successful, would have to be reproducible, high performing and have long-term stability and relatively low energy consumption.

Recently, a new CO2-rich gas-utilizing battery has been developed (which) 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.

(This approach is unique, as we take it, relative to the USDOE's above-cited "syntrolysis" process, in that excess renewable electrical energy is actually stored as chemical energy in the "Li/Ti/Mg" "anode", through reversible oxidation-reduction reactions. At elevated temperatures, as we would have in a stream of syngas derived from Coal and/or Biomass, the metallic element anodes chemically reduce the CO2 and H2O, to form the syngas blend of Carbon Monoxide and Hydrogen. And, the resulting metal oxides are reduced back to the reactive metallic elements by the influx of renewable electricity, with the concurrent generation of Oxygen, driven off the metal oxides in the anode by the renewable electricity, and, which Oxygen can be fed to the syngas generating partial combustion process. It's pretty slick, when you really think about it. We're not real clear on how you "simultaneously" generate "electricity", but, hey, maybe some Coal Country journalist reading this will surprise us by being interested enough to give Dr. Kang a call and ask.) 

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. solid carbon, syngas (CO+H2), O2) have good market values."

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The full Disclosure provides some examples of how the system could be built into, for one instance, an integrated gasification combined cycle, IGCC, Coal-fired power plant, wherein synthesis gas is generated from Coal and then used to generate power - - such configurations, as we understand the literature, enable more efficient separation and capture of both pre- and post-combustion Carbon Dioxide, which, as seen herein, can then be treated as a valuable raw material, in conjunction with some lesser amount of electricity generated by renewable sources.

And, although the syngas resulting from the renewable energy co-electrolysis of CO2 and H2O defined herein could be added to the syngas derived from Coal for power generation purposes, other possibilities are of course also evident, as in the specification that the CO2-based syngas can be used and consumed in the manufacture of, as our subject specifies, liquid fuels like "Methanol" and "Diesel".

A number of other interesting and profitable things, like substitute natural gas Methane, can be made from such syngas, as well.

But, we don't wish to stray too far from the specifics of our subject, "United States Patent 8,658,311- High Temperature Rechargeable Battery for Greenhouse Gas Decomposition and Oxygen Generation", which is a technology invented in West Virginia that could have rather far-reaching importance for the continued, and more profitable, use of West Virginia's far and away most abundant fossil fuel resource: Coal.


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