United States Patent Application: 0140251822
We've presented many reports concerning the development of the Carbon Dioxide recycling and utilization technology known generically as "syntrolysis", wherein CO2 and Water, H2O, are co-electrolyzed, and made thereby to produce, as most often specified, a blend of Carbon Monoxide and Hydrogen; that is, synthesis gas, and, which "syngas" can then be catalytically, chemically condensed, as via for one example the long-known Fischer-Tropsch process, into hydrocarbons - which hydrocarbons are most often specified to be liquids, such as Gasoline, Diesel, Alcohols, and what can be thought of as synthetic Petroleum.
The USDOE, via especially their Idaho National Laboratory, in partnership with the Utah company, Ceramatec, Inc., have been very active in recent years in the development of such CO2-utilization syntrolysis technology, as explained perhaps most succinctly in Ceramatec's US Patent for the "electrochemical cell" needed to conduct syntrolysis reactions, as seen in our report of:
Utah 2011 CO2 + H2O = Hydrocarbon Syngas | Research & Development | News; concerning: "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; 2011; Assignee: Ceramatec, Inc., 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".
However, as seen in our report of:
Utah Recycles CO2 | Research & Development | News; concerning: "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";
Ceramatec has also been developing the technology needed to integrate a "Methanation Reaction" with the Syntrolysis process, so that, instead of, primarily, "liquid fuel for transportation", the total process converts the starting blend of Carbon Dioxide and Water into substitute natural gas Methane.
And, herein we learn, that, just today, the United States Government published Ceramatec's disclosure of their integrated technology for electrochemically converting a blend of Carbon Dioxide and Water into Methane, as well as another valuable gaseous hydrocarbon.
As seen in excerpts from the initial link in this dispatch to:
"United States Patent Application 20140251822 - Production of Valuable Chemicals by Electroreduction of Carbon Dioxide in a Nasicon Cell
September 11, 2014
Inventors: Sai Bhavaraju and James Mosby, Utah
Assignee: Ceramatec, Inc., Salt Lake City
Abstract: A NaSICON cell is used to convert carbon dioxide into a usable, valuable product. In general, this reaction occurs at the cathode where electrons are used to reduce the carbon dioxide, in the presence of water and/or hydrogen gas, to form formate, methane, ethylene, other hydrocarbons and/or other chemicals. The particular chemical that is formed depends upon the reaction conditions, the voltage applied, etc.
(Don't be discouraged by the jargon, "NaSICON". It is, basically, a type of Sodium ion-containing conductive membrane that is, as seen for only one example in:
http://cdn.intechopen.com/pdfs-wm/26705.pdf; "'NASICON Materials:Structure and Electrical Properties'; Lakshmi Vijayan and G. Govindaraj; Department of Physics, School of Physical, Chemical and Applied Sciences, Pondicherry University; Kalapet, India";
known and understood in appropriately-interested enclaves around the world. More can be learned via:
NASICON - Wikipedia, the free encyclopedia.
It is, in sum, available technology.)
Claims: An electrochemical cell comprising: an anode compartment that at least partially houses an anode; a cathode compartment that at least partially houses a cathode; a NaSICON membrane that separates the anode compartment from the cathode compartment, wherein the NaSICON membrane selectively transfers sodium ions from the anode compartment to the cathode compartment during the electrochemical reaction; wherein, during an electrochemical reaction, carbon dioxide is reacted with hydrogen and/or water to form one or more of the following: formate, methoxide, carbon monoxide, methane, ethylene, oxalate, and butane.
The electrochemical cell ... wherein the cathode comprises a gas diffusion electrode.
(The above "gas diffusion electrode", like the "NaSICON" membrane, is, as well, known, understood and currently-utilized technology. See, for background: ": .
Gas diffusion electrode - Wikipedia, the free encyclopedia; "Gas diffusion electrodes (GDE) are electrodes with a conjunction of a solid, liquid and gaseous interface, and an electrical conducting catalyst supporting an electrochemical reaction between the liquid and the gaseous phase".
Further, such electrodes have been refined and further developed for use in such Carbon Dioxide utilization processes, as seen for example in our report of:
New Jersey Improves CO2 Recycling Technology | Research & Development | News; concerning: "United States Patent Application 20130105304 - High Surface Area Electrodes for the Electrodes for the Electrochemical Reduction of Carbon Dioxide; 2013; Assignee: Liquid Light, Inc., NJ; Abstract: Methods and systems for electrochemical conversion of carbon dioxide to organic products including formate and formic acid are provided. A system may include an electrochemical cell including a cathode compartment containing a high surface area cathode and a bicarbonate-based catholyte saturated with carbon dioxide. The high surface area cathode may include an indium coating and having a void volume of between about 30% to 98. The system may also include an anode compartment containing an anode and an acidic anolyte. The electrochemical cell may be configured to produce a product stream upon application of an electrical potential between the anode and the cathode. Background and Field: The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical reduction of carbon dioxide using high surface area electrodes".)
The electrochemical cell ... wherein the cathode compartment is pressurized (and) wherein the carbon dioxide is a gas that is added to the cathode compartment (and) wherein sodium carbonate or sodium bicarbonate is present in the cathode compartment (and wherein the cathode compartment comprises a solvent that at least partially dissolves carbon dioxide.
A method for converting carbon dioxide into a usable chemical comprising; obtaining a quantity of carbon dioxide; placing the carbon dioxide in a cathode compartment of an electrolytic cell, wherein the cell further comprises a NaSICON membrane that separates the cathode compartment from an anode compartment; electrolyzing the cell, wherein the electrolyzing reduces the carbon dioxide and forms one or more of the following: formate, methoxide, carbon monoxide, methane, ethylene, oxalate, and butane.
An electrochemical cell comprising: an anode compartment that at least partially houses an anode; a cathode compartment that at least partially houses a cathode; a NaSICON membrane that separates the anode compartment from the cathode compartment, wherein the NaSICON membrane selectively transfers sodium ions from the anode compartment to the cathode compartment during the electrochemical reaction; wherein, during an electrochemical reaction, carbon dioxide is reacted with at least one of hydrogen and the cathode to form one or more of the following: ethane, ethene, propane, propene, butane, butane, pentane, pentene, hexane, hexane, heptane, heptane, octane, octane, nonane, nonene, decane, decene.
(Note, as above, that, although "methane" and "ethylene" are emphasized in the Abstract, they are far from the only "Valuable Chemicals" that can be synthesized via the technology of our subject from Water and Carbon Dioxide. - JtM)
The electrochemical cell ... wherein the cathode comprises a molten alkali metal (and) wherein the cathode compartment is pressurized (and) wherein carbon dioxide comprises a gas that is added to the cathode compartment.
The electrochemical cell ... wherein hydrogen comprises a gas that is added to the cathode compartment.
A method for converting carbon dioxide into a usable chemical comprising; obtaining a quantity of carbon dioxide; placing the carbon dioxide in a cathode compartment of an electrolytic cell, wherein the cell further comprises a NaSICON membrane that separates the cathode compartment from an anode compartment; electrolyzing the cell, wherein the electrolyzing produces a molten alkali metal that reduces the carbon dioxide and forms one or more of the following: ethane, ethene, propane, propene, butane, butane, pentane, pentene, hexane, hexane, heptane, heptane, octane, octane, nonane, nonene, decane, decene.
Background: Carbon dioxide (CO2) is a naturally occurring chemical that is found in the atmosphere. This chemical is also produced as a byproduct in many chemical processes. Because of its natural abundance, it is readily available and inexpensive.
Summary: The present embodiments relate to using a NaSICON (or other similar type electrochemical cell) as a means of "fixing" CO2-- e.g., converting the CO2 into a valuable chemical, such as a hydrocarbon fuel, ..., etc. In general, this conversion reaction will occur in the cathode side of a NaSICON cell. As known in the industry, the NaSICON membrane will separate the cell into an anode compartment and a cathode compartment. Thus, the carbon dioxide will be reacted with an alkali metal, hydrogen gas and/or water in the cathode compartment (along with electrons) such that the carbon dioxide is fixed and converted into a usable product.
Because the NaSICON membrane isolates the cathode compartment from the anode compartment, specific advantages are obtained. These advantages include:
- two separate environments for different reaction conditions--for example, the anolyte may be non-aqueous, while the catholyte is aqueous (and vice versa);
- anolyte may be at a higher temperature than the catholyte (and vice versa);
- anolyte may be pressurized and catholyte not (and vice versa);
- anolyte may be irradiated and catholyte not (and vice versa);
- anolyte and/or anode may be designed to conduct specific reactions that are not dependent upon the catholyte and/or cathode reactions (and vice versa);
- the different chambers may have different flow conditions, solvents, solubilities, product retrieval/separation mechanisms, polarities, etc. The ability to have separate reaction conditions in the anolyte compartment and catholyte compartment may allow the reactions in each compartment to be tailored to achieve optimal results.
Generally, any desired or chosen reaction may occur in the anode compartment of the cell, provided that there is an electrolyte within the anode compartment that includes alkali metal ions (sodium ions) that will transport across the membrane (e.g., the NaSICON membrane) and enter the cathode compartment. Some of these compounds include NaOH, (Sodium Hydroxide - Lye); NaCl (Salt), Na2CO3 (Sodium Carbonate, and), etc.
(Depending) upon the particular reactants, voltages, conditions, etc., the present embodiments operate to convert carbon dioxide into one or more of the following chemicals (in an electrochemical cell):
- formate;
- methoxide;
- carbon monoxide;
- methane;
- ethylene;
- oxalate;
- paraffinic and olefinic hydrocarbons (such as butane or butene)".
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The reaction examples provided by Ceramatec in the full Disclosure seem generally specify the addition of elemental, molecular Hydrogen, although Water as the source of the Hydrogen is as often specified. Our take is that the Hydrogen generation, via catalyzed electrolysis from Water, is, or could be, an integral part or component of the CO2 utilization process, as it is in Ceramatec's above-cited "US Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water".
And, earlier, somewhat related electro-synthesis processes utilizing Carbon Dioxide and Water, as in:
Chicago Converts CO2 into Methane and Ethylene | Research & Development | News; concerning: "United States Patent 4,897,167 - Electrochemical Reduction of CO2 to CH4 (Methane) and C2H4 (Ethylene); 1990; Assignee: Gas Research Institute, Chicago; Abstract: A process for electrochemical reduction of CO2 to CH4 and C2H4 providing both high current densities and high Faradaic efficiencies. The process is carried out in an electrochemical cell wherein copper is electrodeposited in situ on the cathode surface making freshly deposited copper available for the electrochemical reduction. Faradaic efficiencies of about 75 to about 98 percent for production of CH4 and C2H4 are obtained";
wherein similar key products, i.e., methane and ethylene, are obtained, clearly define that the Hydrogen can be concurrently extracted from H2O as a component operation of the overall process.
Regardless, as we've seen in other reports, such as:
North Carolina Sunshine Extracts Hydrogen from H2O for USDOE | Research & Development | News; concerning: "US Patent 8,524,903 - Ruthenium or Osmium Complexes and Their Uses as Catalysts for Water Oxidation; 2013; Assignee: The University of North Carolina at Chapel Hill; Abstract: The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules. Government Interests: This invention was made, in-part, with United States government support under grants numbered DE-FG02-06ER15788 and DE-SC0001011 from the Department of Energy. The U.S. Government has certain rights to this invention. ... Background and Field: The present invention generally relates to catalysts for water oxidation. Hydrogen is one of the most promising alternative energy sources. It can be obtained by electrolysis of water, which is environmentally friendly and efficient. However, the electrolysis of water is an energy intensive process, which is very expensive. On the other hand, photolysis, the splitting of water by light, presents an attractive alternative method of obtaining hydrogen. Additionally, light driven reduction of carbon dioxide by water to provide hydrocarbons or methanol may be another promising alternative to alternate energy sources";
the technology is being developed to evolve elemental Hydrogen from H2O, in efficient processes which can be powered by freely-available sunlight, specifically for such chemical "reduction of carbon dioxide by water to provide hydrocarbons".
In any case, as disclosed herein by an accomplished developer of Carbon Dioxide utilization technologies, a partner of the USDOE, the Carbon Dioxide that arises in only a small way - - relative to some all-natural and un-taxable sources of it's emission, such as the Earth's inexorable processes of planetary volcanism - - from our economically essential use of Coal in the generation of abundant, reliable and affordable electric power, could and should be seen and treated as a valuable raw material resource.
We can reclaim "readily available and inexpensive" Carbon Dioxide from whatever source most convenient to us, and then use that Carbon Dioxide as the basic raw material for the synthesis of an array of "Valuable Chemicals", including Ethylene and substitute natural gas Methane.