United States Patent Application: 0120048730
We remind you of our many reports concerning the development of what was at one time referred to as "Syntrolysis", that is, the co-electrolysis of Carbon Dioxide, CO2, and Water, H2O, in order to generate a hydrocarbon synthesis gas consisting of Carbon Monoxide, CO, and Hydrogen, H2, along with byproduct Oxygen, O2, by one or two of our United States Department of Energy's western National Laboratories and their contractor, Ceramatec, Inc., of Salt Lake City, Utah.
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. Conclusion: Based on the results obtained to date, coelectrolysis of steam and carbon dioxide for direct production of syngas appears to be a promising technology that could provide a possible path to reduced greenhouse gas emissions and increased energy independence, without the infrastructure shift that would be required for a hydrogen-based transportation system";
the purpose of developing a technology for "producing syngas by simultaneous electrolytic reduction of steam and carbon dioxide" was so that the resultant Carbon Monoxide and Hydrogen could then "be used for the production of synthetic liquid fuels via Fischer-Tropsch processes".
Those efforts have led, 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"; and:
West Virginia Coal Association | Utah 2012 CO2 + H2O = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent Application 20120043219 - Electrochemical Process for the Production of Synthesis Gas Using Atmospheric Air and Water; February 23, 2012; Inventors: Joseph Hartvigsen, et. al., Utah; (Assignee: Ceramatec, Inc., Salt Lake City); 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";
to what we would think to be some exciting developments for anyone at all concerned with either or both United States energy security, especially in terms of our supply of liquid hydrocarbon fuels, and the atmospheric accumulation of Carbon Dioxide.
We remind you, as well, that, as might be suggested by our report of:
West Virginia Coal Association | USDOE 1976 Atmospheric CO2 to Methanol | Research & Development; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Inventor: Meyer Steinberg, NY; Assignee: The USA as represented by the USDOE; Abstract: A method and system 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. Summary: In accordance with a preferred embodiment of this invention, a solution of KOH is employed to absorb CO2 from air forming an aqueous solution of K2CO3, the solution is then electrolyzed to produce CH3OH (i.e., Methanol) and reform KOH in solution, the CH3OH is then removed, and make-up water is then added prior to repeating the aforementioned steps. Other products ... are also formed which can be separated and recovered as valuable products. By the process described above, it is seen that any source of electrical power may be employed, such as coal-fired power plants. However, from an environmental point of view ... solar energy generated power, would be preferred";
the USDOE's and Ceramatec's efforts likely arose from earlier work undertaken by the USDOE and it's precedent agencies on the electrochemical conversion of liquid CO2 and H2O directly into alcohol. And, their later work might well have centered on the generation, instead of alcohol, of synthesis gas, since the "Fischer-Tropsch processes", which consume "syngas", enable the direct production of more conventional liquid, and gaseous, hydrocarbons, as opposed to just alcohols, like Methanol.
However, as seen for one example in our report of:
West Virginia Coal Association | Columbia University Practical Extraction of Atmospheric CO2 | Research & Development; concerning: "United States Patent 8,246,731 - Systems and Methods for Extraction of Carbon Dioxide from Air; 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 solution comprising a base - - resulting in 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 ... further comprising a supply of basic solution in fluid connection with said wet scrubbing mechanism (and) wherein the base material included in said basic solution is selected from sodium hydroxide, calcium hydroxide, and potassium hydroxide";
the cyclic use of metal compunds, like "potassium hydroxide", the "KOH" of "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2" and chemically very closely-related "sodium hydroxide", NaOH, and, after absorption of Carbon Dioxide, the carbonates of those metals, to efficiently extract Carbon Dioxide, even from the atmosphere itself, is becoming more sophisticated and more efficient. And, they could be made even more efficient if the CO2 bound in the carbonate solutions could be utilized, again as in "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2", without having to expend the energy to first extract the CO2 from the carbonate solutions, as would seem to be necessitated by Ceramatec's process of "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water", although, as seemingly indicated in Ceramatec's "United States Patent Application 20120043219 - Electrochemical Process for the Production of Synthesis Gas Using Atmospheric Air and Water", "synthesis gas" can be generated "from carbon dioxide obtained from atmospheric air or other available carbon dioxide source and water using a sodium-conducting electrochemical cell", it might not be necessary to expend the energy to either first separate the CO2 from a saturated carbonate solution or to generate the steam.
And, herein, Ceramatec confirms that the more versatile, more valuable synthesis gas blend of Carbon Monoxide and Hydrogen can be directly and more efficiently generated from what we would take to be a saturated Carbon Dioxide scrubbing solution in the liquid phase; although performing the operation in the gaseous phase remains an option, as well. As seen in excerpts from the initial link in this dispatch to:
"United States Patent Application 2020048730 - Electrochemical Cell for the Production of Synthesis Gas Using Atmospheric Air and Water
(Note that we take this to be an advancement on the earlier, but almost indentically-titled, "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water", about which, as per our above citations, we earlier reported.)
Date: March 1, 2012
Inventors: Joseph Hartvigsen, et. al., Utah
(As we have earlier noted, the eventual Assignee of Rights, if different from the named inventors, is often not published in early versions of US Patent Applications. However, as can be learned in supporting documentation for our subject, "US Patent Application 2020048730", such as that accessible via:
it is clear that the eventual Assignee of Rights to any patent issuing from this application will be Ceramatec, Inc., of Salt Lake City, UT.)
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.
Claims: An electrochemical cell for producing synthesis gas comprising: an anode chamber comprising an electrochemically active anode and a source of water in which the water is decomposed (and) wherein O2 is collected and removed from the anode chamber and wherein the anode chamber has a source of entry for Na2CO3 at a sufficient distance away from the anode such that the Na2CO3 reacts with H+ in solution (and) wherein CO2 is collected and removed at a location spaced apart from the anode where O2 is collected and removed;
(Note that Carbon Dioxide can be extracted from a Sodium Carbonate, "Na2CO3", solution not just by heating it, but, also by reacting the carbonate with Hydrogen ions.)
- a cathode chamber comprising an electrochemically active cathode separated from the anode chamber by a membrane which permits transport of Na+ ions, wherein the cathode chamber has a source of water and Na+ ions, in which the water is decomposed according to the following reaction: Na+ + H2O + e-= NaOH +1/2H2, wherein H2 is collected and removed from the cathode chamber and wherein NaOH is collected and removed from the cathode chamber; and means for facilitating the reaction of CO2 and H2 to form synthesis gas comprising CO and H2.
(Note that, by multiple chemical and electrochemical pathways, relatively more Hydrogen than is needed for the syngas composition is being generated. Surplus Hydrogen can then be reacted, according to the reverse water gas shift, or reverse conversion, reaction, as described 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; Inventor: Rene Dupont, et. al., France; Assignee: Air Liquide; Abstract: The invention concerns a method for producing carbon monoxide by reverse conversion, in gas phase, of carbonic acid gas and gaseous hydrogen";
with more Carbon Dioxide to make more of the desired Carbon Monoxide.)
The electrochemical cell ... wherein the source of Na2CO3 comprises Na2CO3 obtained by reacting the NaOH removed from the cathode with a source of CO2.
(And) wherein the source of CO2 is atmospheric air (or) the source of CO2 is combustion gases.
The electrochemical cell ... wherein the means for facilitating the reaction of CO2 and H2 to form synthesis gas comprises a catalyst exposed to the mixture of CO2 and H2.
(The above is as in our earlier citation of "United States Patent Application 20030113244 - Method for Producing Carbon Monoxide by Reverse Conversion with an Adapted Catalyst". )
The electrochemical cell ... wherein the catalyst comprises a watergas shift catalyst.
(The "watergas shift" reaction, H2O + CO = CO2 + H2, is apparently employed in the sequence as well as the reverse water gas shift, or reverse "conversion", CO2 + H2 = CO + H2O.)
The electrochemical cell ... wherein the catalyst comprises a Fischer-Tropsch catalyst.
(Fischer–Tropsch process - Wikipedia, the free encyclopedia; "The Fischer–Tropsch process is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogenn into liquid hydrocarbons. It was first developed by Franz Fischer and Hans Tropsch (in Germany) in 1925. The process ... produces a synthetic lubrication oil and synthetic fuel, typically from coal".)
The electrochemical cell (including) the means for facilitating the reaction of CO2 and H2 to form synthesis gas further comprises an oxygen ion conducting electrolysis cell to cause electrolysis of CO2 to form CO, which is mixed with H2 to produce synthesis gas.
(As we've reported, for instance in:
West Virginia Coal Association | Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development; concerning: "US Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes; 1987; Assignee: The Standard Oil Company; Abstract: A process for the electrocatalytic reduction of carbon dioxide comprises immersing a transition metal complex with square planar geometry into an aqueous or nonaqueous solution which has been acidified to a (specified) hydrogen ion concentration ... , adding the carbon dioxide, applying an electrical potential of from about -0.8 volts to about -1.5 volts ... , and reducing the carbon dioxide to carbon monoxide";
the direct and energy-efficient catalyzed electrolytic reduction of Carbon Dioxide to Carbon Monoxide is known and established technology.)
The electrochemical cell ... wherein the electrochemical cell is embodied within a plurality of stacked electrochemical cells separated by bipolar plates (and) wherein the membrane which permits transport of Na+ ions comprises a sodium super ionic conductor ceramic material.
(Concerning the immediately above, keep in mind, that, as can be learned via:
Advanced Ceramics Material Technology Research & Development » Ceramatec; "Ceramatec: Advanced Ceramics Material Technologies Research & Development Company; Ceramatec's advanced ceramics material technology research and development focus is primarily in energy & environment (cleantech) areas";
the intended Assignee of Rights to this invention, and the employer of the inventors, is primarily concerned with the development and production of the necessary specialty "ceramic material"s with which the Carbon Dioxide-converting "electrochemical cell" of our subject, "United States Patent Application 2020048730 - Electrochemical for the Production of Synthesis Gas Using Atmospheric Air and Water", is constructed. As much as anything, they are establishing, through their CO2-conversion technologies, a larger market for their basic ceramic products and technologies.)
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.
Users of fuels such as gasoline and diesel (in commercial applications) and JP-8, F-76 and other similar fuels (in military applications) have benefited from the existence of an extensive and well-established infrastructure for their shipping, delivery to end users, and use. The presence of this infrastructure has also enabled technology development of liquid fuel-based systems for uses ranging from automobiles to military aircraft. Within areas well-served by this infrastructure, dependence upon such liquid fuel-based systems is largely unquestioned.
As a result, 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 and Description: 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.
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.
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.
(Gas phase electrolysis of CO2 and H2O as well as liquid phase electrolysis is envisioned in this Disclosure, as they both are in the above-cited "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water", although the liquid phase seems to predominate in the exposition of it, as per our introductory comments, and despite some examples of embodiments.)
A source of steam and carbon dioxide may contact the cathode under conditions which cause the following reactions to occur: H2O + 2e = H2 + O2, 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.
(Materials of the electrode construction are specified. Though some are moderately exotic, they are all well-known and obtainable within North America.)
The source of carbon dioxide is preferably selected from atmospheric air, combustion gases, or aerobic decomposition gases.
This syngas (as produced as above) can be further processed to produce liquid hydrocarbon fuel using any suitable process available in the art. One such process commonly used to convert syngas to liquid fuel is the Fischer-Tropsch process, in which syngas is reacted in the presence of a catalyst (such as an iron or cobalt catalyst) to produce liquid hydrocarbon fuels. Other suitable processes, including variations on the Fischer-Tropsch process, are known to those of ordinary skill in the art, and could be used with the processes of the present invention. Here the term liquid hydrocarbon fuel also includes lighter hydrocarbons such as methane, ethane, propane, butane, etc. which may be vapors at ambient conditions but which also may be liquefied under pressure or cryogentic conditions. A typical Fischer-Tropsch process produces a wide distribution of hydrocarbon chain length, all having fuel value.
In another embodiment within the scope of the present invention, a three-compartment electrochemical cell is provided (and) a plurality of three-compartment electrochemical cells, separated by bipolar plates, may be stacked or connected in a way to efficiently generate large quantities of carbon dioxide and hydrogen for use in producing synthesis gas."
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So, basically, starting with Carbon Dioxide, as recovered from whatever convenient source, and Water, which is a continuously renewable commodity for industrial purposes even though insidious types of pollution might threaten our supplies of drinking water, we can produce a "syngas" composed of Carbon Monoxide and Hydrogen, which syngas, through known "variations on the Fischer-Tropsch process", can be converted into "liquid fuel" and into "lighter hydrocarbons such as methane, ethane, propane, butane, etc.".
Now, since, as seen for only one out of many possible examples in:
Mountaineer Wind Energy Center - Wikipedia, the free encyclopedia; concerning: "Mountaineer Wind Energy Center is a wind farm on Backbone Mountain in Preston and Tucker counties in the U.S. state of West Virginia. When it came online in December 2002, Mountaineer was the first wind farm in West Virginia, and the largest east of the Mississippi River"; and, as emphasized in:
Wind Energy: A West Virginia Business Opportunity; "While coal is and will continue to be the principal energy resource for making electricity in West Virginia, wind energy is also becoming a player as well. West Virginia is home to four wind farms: the 66 MW Wind Energy Center in Tucker County, the 264 MW NedPower project in Grant County and the 100 MW Beech Ridge project in Greenbrier County and the 98 MW Laurel Mountain project in Barbour/Randolph counties. An additional 365 MW of wind electrical generation capacity have been permitted and are under development in West Virginia";
we do have some opportunities in Coal Country where we could both generate a little supplemental electricity from wind, and, as in our above-cited report concerning "United States Patent 8,246,731 - Systems and Methods for Extraction of Carbon Dioxide from Air", have an increasingly-valuable raw material resource, Carbon Dioxide, brought to us on that wind, it seems to us here that we have in hand a combination of circumstances which we could put together, in conjunction with the electrolytic process of our subject herein, "US Patent Application 2020048730 - Electrochemical Cell for the Production of Synthesis Gas Using Atmospheric Air and Water", and thereby accomplish a number of seemingly-desirable things, i.e.:
Free our absolutely economically essential Coal-based power generation facilities from the venal threat of Cap & Trade carbon taxation; Put more Coal Country citizens to work; Reduce, or at least help to, by displacing virgin petroleum fuels, stabilize the concentrations of CO2 in our atmosphere; and, stick a big old finger, with Coal dust grimed under it's nail, into OPEC's eye.
Is there anything not to like about any of that? No? Then why aren't we at least openly and publicly disclosing and discussing the possibilities?