United States Patent Application: 0120043219
Herein, we provide further confirmation of the fact, that, Carbon Dioxide, as it is co-produced in a small way, relative to some natural sources of emission, such as the Earth's inexorable processes of planetary volcanism, from our economically essential use of Coal in the generation of abundant and truly affordable electric power, can be, we assert should be, seen and treated as a valuable raw material resource.
We remind you of our previous reports concerning the process of "syntrolysis"; that is, the co-electrolysis of Carbon Dioxide and Steam, H2O, which results in the production, in addition to byproduct Oxygen, of a blend of Carbon Monoxide and Hydrogen; which CO and H2 comprise a synthesis gas, or syngas, suitable for catalytic chemical condensation, as via the long-known Fischer-Tropsch synthesis, into both liquid and gaseous hydrocarbons.
The initial technical development of syntrolysis had been taking place at our United States Department of Energy's Idaho National Laboratory, 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. 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".And note, in the above, participation in the development of the technology by the Utah company, Ceramatec, who, as seen in:
West Virginia Coal Association | Utah Recycles CO2 | Research & Development; concerning their independent report: "Co-Electrolysis of Steam and Carbon Dioxide as Feed to a Methanation Reaction;
Lyman Frost, Joseph Hartvigsen and S. Elangovan; Ceramatec, Inc, Salt Lake City, UT; Abstract:
Solid oxide fuel cells can be operated in reverse by applying an electric potential across the fuel cells and forcing the oxygen ion to flow in the opposite direction from the fuel cell mode. If a mixture of high temperature steam and carbon dioxide are fed to a fuel cell stack operating in this electrolysis mode, the result will be a mixture of carbon monoxide and hydrogen. By adjusting the input ratios of steam and carbon dioxide, the output of the electrolysis system can be modified to be in the proper ratio for the formation of a number of different hydrocarbons by catalytic process through either Fischer Tropsch or methanation reactions. This paper will report on work being done at Ceramatec on use of proprietary Ceramatec solid oxide fuel cell materials operating in a high temperature electrolysis mode. . The paper will report on the durability of the materials in this endothermic mode of operation and will provide data on the variation in percentages of output gases (synthesis gas) dependent on the input gas stream. The operation of a small methanation reactor on the synthesis gas will be described and the reaction results will be documented and reported";
have conducted their own, independent research and development devoted to the production of a "synthesis gas" from Carbon Dioxide and H2O, which syngas can be used in the synthesis of substitute natural gas Methane, as in "methanation reactions", as well as, via "Fischer Tropsch" technology, liquid hydrocarbons; and which independent work resulted in, as seen via:
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; Date: December 13, 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";
the design of what some have called a "reverse fuel cell" for the conversion of Carbon Dioxide and H2O, via an efficient co-electrolysis, into such hydrocarbon synthesis gas.
So close has been the cooperation between our USDOE and Ceramatec, in fact, that, as can be seen in the full document about which we most recently reported in:
West Virginia Coal Association | USDOE Converts More CO2 into Hydrocarbon Syngas | Research & Development; concerning: "'United States Patent 7,951,283 - High Temperature Electrolysis for Syngas Production'; Date: May 31, 2011; Inventor: Carl Stoots, et. al., Idaho; Assignee: Battelle Energy Alliance (Idaho National Laboratory; USDOE); Abstract: Syngas components hydrogen and carbon monoxide may be formed by the decomposition of carbon dioxide and water or steam by a solid-oxide electrolysis cell to form carbon monoxide and hydrogen, a portion of which may be reacted with carbon dioxide to form carbon monoxide ... . Government Interests: This invention was made with government support under DE-AC07-05ID14517 awarded by the United States Department of Energy. The government has certain rights in the invention. Claims: A method for producing at least one syngas component (from) water and carbon dioxide (in a) solid-oxide electrolysis cell (and) further comprising routing the hydrogen and the carbon monoxide to a synfuel production process";
Ceramatec's Joseph Hartvigsen, lead named inventor of Ceramatec's "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water", is named, though not reflected in our excerpts from it, as a co-inventor of the above "United States Patent 7,951,283 - High Temperature Electrolysis for Syngas Production", even though Ceramatec itself isn't openly named, or assigned any share of the rights to that invention.
And, herein, we learn that Hartvigsen and his Ceramatec colleagues have continued in their independent development of "syntrolysis", CO2-H2O co-
As seen in excerpts from the initial link in this dispatch to:
"United States Patent Application 20120043219 - Electrochemical Process for the Production of Synthesis Gas Using Atmospheric Air and Water
Date: February 23, 2012
Inventors: Joseph Hartvigsen, et. al., Utah
(As we have noted several times in past reports, the eventual Assignee of Rights to United States Patents, if different from the name inventor(s), is often not identified in, especially early published versions of, United States Patent Applications, as is the case herein. However, supporting documentation accompanying "United States Patent Application 20120043219" in the US Patent and Trademark files, as accessible via:
http://assignments.uspto.gov/
clearly identifies Ceramatec, Inc., of Salt Lake City, UT, as the eventual Assignee of Rights, if and when a United States patent issues from "Application 20120043219".
Further, the CO2-recycling invention disclosed via this patent application relates to a chemical process and processing equipment design that might better be understood through graphic presentation. To that end, we enclose two links, following:
which, if they maintain their functionality, they might not, should take you to documents that are a part of "United States Patent Application 20120043219", and which provide graphical presentations of the disclosed process. Clearly illustrated is the transformation of CO2 and H2O into Carbon Monoxide and Hydrogen, with byproduct Oxygen being extracted.
Even further: This US Patent Application is only the first of several related and similar concerning this specific type of Carbon Dioxide recycling technology that have been made by Ceramatec, and published by the US Patent and Trademark Office. We were going to include some mention of others herein; but, the CO2 utilization technologies embodied within them is so complete and so thorough, that our inclusion of any of them would have made the presentation confusing and overlong. As will become clear in reports to follow, a rather complete technical process and system for the efficient, combined electro-chemical and thermo-chemical conversion of Carbon Dioxide and Water into Hydrocarbons and Oxygen has be devised by Joe Hartvigsen and his colleagues at Ceramatec; which complete process is founded on, and evolved from, the "Syntrolysis" technology first established at the USDOE's Idaho National Laboratory.
And, even further: As we've touched on in a few previous reports, the "Syntrolysis"-type CO2-recycling technology has also been acknowledged and further developed by other researchers elsewhere in the world; and, those foreign developments are as well proceeding, as we will also document in future reports.)
Abstract: A process 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.
Claims: An electrochemical process for producing synthesis gas comprising: decomposing water within an anode chamber comprising an electrochemically active anode according to the following reaction:
1/2H2O = 1/4O2 + H (ions); removing oxygen from the anode chamber; transporting H+ ions from the anode chamber to an intermediate chamber; reacting Na2CO3 and H.+ ions within the intermediate chamber (to extract CO2, regenerate Sodium (further) decomposing water within the cathode chamber comprising an electrochemically active cathode according to the following reaction: (Sodium + H2O = Sodium Hydroxide and Hydrogen) and reacting CO2 and H2 to form synthesis gas comprising CO and H2.
The electrochemical process ... wherein the NaOH removed from the cathode is reacted with a source of CO2 to form Na2CO3.
(The use of a Sodium Hydroxide, Lye, "NaOH", and Sodium Carbonate, "Na2CO3", cycle for the regenerative and repetitive chemical capture of CO2 from gas streams and it's subsequent release is, in one type of CO2 scrubber or another, often specified; as seen for one example in our report of:
West Virginia Coal Association | Columbia University August 2012 Practical CO2 Air Capture | Research & Development; concerning: "United States Patent 8,246,731 - Systems and Methods for Extraction of Carbon Dioxide from Air; 2012; Assignee: The Trustees of Columbia University in the City of New York; Abstract: The present invention describes methods and systems for extracting, capturing, reducing, storing, sequestering, or disposing of carbon dioxide (CO2), particularly from the air. The CO2 extraction methods and systems involve the use of chemical processes. Methods are also described for extracting and/or capturing CO2 via exposing air containing carbon dioxide to - - a basic solution which absorbs carbon dioxide and produces a carbonate solution. The solution is causticized and the temperature is increased to release carbon dioxide, followed by hydration of solid components to regenerate the base. ... The system ... wherein the base material is sodium hydroxide (and) wherein the carbonate solution is a sodium carbonate (Na2CO3) solution".However, in the case of our subject herein, "US Patent Application 20120043219 - Electrochemical Process for the Production of Synthesis Gas Using Atmospheric Air and Water", rather than the "sodium carbonate (Na2CO3)" being "causticized and the temperature ... increased to release carbon dioxide", in a known and established reaction process an excess of Hydrogen is used to extract CO2 from Na2CO3 and regenerate the NaOH absorbent.)
The electrochemical process ... wherein the source of CO2 is selected from atmospheric air, combustion gases, or aerobic decomposition gases.
An electrochemical process for producing synthesis gas comprising: decomposing water within an anode chamber according to the following reaction: 1/2H2O = 1/4O2 + H(+); removing oxygen from the anode chamber; reacting Na2CO3 and H(+) ions within anode chamber (to yield CO2, H2O and Na+); removing CO2 from the anode chamber at a location near where it is produced; transporting Na.+ ions from the anode chamber to a cathode chamber; decomposing water within the cathode chamber according to the following reaction: Na + H2O = NaOH + 1/2H2; removing H2 from the cathode chamber; removing NaOH from the cathode chamber; and reacting CO2 and H2 to form synthesis gas comprising CO and H2.
(The process is directed to generating an excess of Hydrogen, some of it via the reaction of Sodium, Na, metal regenerated in the electrolytic segment of the process with Water, H2O; which in turn releases Hydrogen and regenerates some of the NaOH that absorbs the Carbon Dioxide. We'll trust that everyone remembers their high school chemistry, where the teacher dropped a small lump of Sodium metal into a beaker of water, and then lit the gas, Hydrogen, which began bubbling out of the beaker. Sodium is reactive enough to break apart the Water molecule.
Further, as regards "reacting CO2 and H2 to form synthesis gas comprising CO and H2", Ceramatec are referring to the "reverse water gas shift" or, more simply, "reverse conversion" reaction discussed, for one example, in our report of:
West Virginia Coal Association | France Efficient CO2 to Carbon Monoxide Conversion | Research & Development; concerning: "'United States Patent Application 20030113244 - Method for Producing Carbon Monoxide by Reverse Conversion with an Adapted Catalyst'; 2003; Assignee: Air Liquide; (France); Abstract: The invention concerns a method for producing carbon monoxide by reverse conversion, in gas phase, of carbonic acid gas and gaseous hydrogen while minimising the production of methane".)
The electrochemical process ... wherein the NaOH removed from the cathode is reacted with a source of CO2 to form Na2CO3 (and) wherein the source of CO2 is selected from atmospheric air, hydrocarbon combustion gases, or aerobic decomposition gases.
Background and Field: The present invention relates in general to methods for producing synthesis gas from easily obtainable precursors, and more particularly, to the generation of such synthesis gas from atmospheric air and water.
(It) is anticipated that reliance upon liquid fuel-based systems will continue well into the foreseeable future. It would thus be beneficial to provide new methods and systems for generating liquid fuels using electricity and commonly-available resources ... . Such methods and systems are provided herein.
Summary: The present invention is directed to processes, methods, and systems for the production of synthesis gas for fuel production or other applications. The processes, methods, and systems of the present invention utilize commonly-available resources as inputs and rely upon electricity to provide synthesis gas as an output.
The present invention includes an electrochemical cell for producing synthesis gas. In one embodiment within the scope of the invention, the electrochemical cell includes an anode chamber containing an electrochemically active anode. Water is decomposed at the anode to produce oxygen and hydrogen ions. The oxygen is preferably collected and removed from the anode chamber. A source of sodium carbonate is provided which reacts with the hydrogen ions and decomposes to form carbon dioxide, water, and sodium ions.
The carbon dioxide is preferably collected and removed.
The electrochemical cell includes a cathode chamber containing an electrochemically active cathode separated from the anode chamber, or intermediate chamber, by a membrane which permits transport of Na+ ions. The membrane which permits transport of Na+ ions is preferably a sodium super ionic conductor ceramic material, a cation exchange membrane, or other similar membrane.
Water is reduced in the cathode chamber to produce hydrogen gas and hydroxyl ions. The hydroxyl ions combine with sodium ions to form sodium hydroxide.
The hydrogen gas is collected and removed from the cathode chamber.
The system or process includes means for facilitating the reaction of CO2 and H2 to form synthesis gas comprising CO and additional H2. Such means may include a catalyst exposed to the mixture of CO2 and H2. The catalyst may be a watergas shift catalyst or a Fischer-Tropsch catalyst. The mixture of CO2 and H2 may alternatively be heated to enable a homogenous gas phase equilibrium reaction with CO and H2O. The means for facilitating the reaction of CO2 and H2 to form synthesis gas may include an oxygen ion conducting electrolysis cell to cause electrolysis of CO2 to CO, which with the H2 comprises synthesis gas.
(Note, that, in addition to the reverse conversion, as in the above-cited 'United States Patent Application 20030113244 - Method for Producing Carbon Monoxide by Reverse Conversion with an Adapted Catalyst", some of the Carbon Monoxide is produced herein from Carbon Dioxide via direct electrolysis.)
In the foregoing embodiment, sodium hydroxide is preferably removed from the cathode and reacted with a source of carbon dioxide to form sodium carbonate which may replenish the sodium carbonate decomposed in the anode chamber. The source of carbon dioxide includes, but is not limited to atmospheric air, combustion gases, and aerobic decomposition gases.
The electrochemical cell may be embodied within a plurality of stacked electrochemical cells separated by bipolar plates. The use of stacked electrochemical cells may enable the efficient production of large quantities of synthesis gas.
Another embodiment within the scope of the invention includes an electrochemical device for the coelectrolysis of carbon dioxide and steam to produce synthesis gas. This electrochemical device includes an oxygen ion conducting membrane, a cathode attached to one surface of the oxygen ion conducting membrane and an anode attached to an opposite surface of the oxygen ion conducting membrane. The cathode is electrochemically active for reduction of steam to form hydrogen and oxygen ions. The anode is electrochemically active for recombination of oxygen ions into oxygen molecules.
A source of steam and carbon dioxide may contact the cathode under conditions which cause the following reactions to occur: H2O + 2e- = H2 + O2 (and) CO2 + 2e =.CO + O2 and CO2 + H2 = CO + H2O.
Synthesis gas comprising CO and H2 is collected and recovered at the cathode, and oxygen ions are conducted through the oxygen ion conducting membrane to the anode where they are recombined to form O2, which is collected and recovered."
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Keep in mind that the byproduct "O2, which is collected and recovered" is a commodity of commercial value, the sale of which
- - perhaps for use in a process like that disclosed in our report of:
West Virginia Coal Association | USDOE Hydrogasifies Coal, Recycles Carbon | Research & Development; concerning: "United States Patent 3,988,123 - Gasification of Carbonaceous Solids; 1976; Assignee: The United States of America; The invention described herein was made in the course of Contract E(49-18)-1548 with the U.S. Energy Research and Development Administration. Abstract: A process and apparatus for converting coal and other carbonaceous solids to an intermediate heating value fuel gas or to a synthesis gas. A stream of entrained pulverized coal is fed into the combustion stage of a three-stage gasifier along with a mixture of oxygen and steam at selected pressure and temperature";wherein it could be used to support the conversion of by far our most abundant fossil energy resource into even more hydrocarbon "synthesis gas", much like that generated via the process of our subject herein,
"United States Patent Application 20120043219 - Electrochemical Process for the Production of Synthesis Gas Using Atmospheric Air and Water", from Carbon Dioxide and Water, which "synthesis gas ... may then be further processed and eventually converted into a liquid fuel suitable for transportation" - -
could help to offset or to reduce the effective costs of producing, as via the process of our subject herein,
"United States Patent Application 20120043219 - Electrochemical Process for the Production of Synthesis Gas Using Atmospheric Air and Water", a "Synthesis gas comprising CO and H2" from nothing but Water and that old green house devil, Carbon Dioxide.
And, in closing, we refer again to our above-cited report 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"; wherein it's affirmed, that: "a mixture of hydrogen and carbon monoxide" as produced herein, via an "Electrochemical Process", from Carbon Dioxide and Water, or as produced via the above-cited process of "United States Patent 3,988,123 - Gasification of Carbonaceous Solids", from Coal, "can be used for the production of synthetic liquid fuels via Fischer-Tropsch processes".
As we will see in reports to follow, not only has Ceramatec further applied themselves to improving and refining the process of generating such mixtures "of hydrogen and carbon monoxide" from Carbon Dioxide and Water, they have, as well, applied themselves to improving and refining the "Fischer-Tropsch processes" for the further conversion of their Carbon Dioxide-based "Syngas" into "synthetic liquid fuels".