This past June, we began redressing some slights in our reportage, concerning the development of technologies that enable the efficient conversion of Carbon Dioxide, as reclaimed from whatever handy domestic US source, into the sorts of things, i.e., liquid hydrocarbon fuels, we US citizens, with a decorously minimal amount of sniveling, fork over the better part of five bucks a gallon for to OPEC and their multinational Big Oil front men.
The sheiks can't afford to buy enough toe rings for their harem girls, we guess; at least while their funding jihad. Nor, we suppose, can the gold plating on the bumpers of all the cowboys' Cadillacs ever be thick enough. And, we hard-working stiffs in US Coal Country do understand how tough it is for everyone to get by in the style to which they've become accustomed; we are always willing, it seems, to share what we have in order to ensure that they are able to do so.
Even with Uncle Sam.
We seem willing to contemplate electric bills grossly inflated by Cap and Trade carbon taxes; with our good Uncle perhaps needing the extra income to buy another carrier group or two to help keep the Strait of Hormuz open for the convenience of Big Oil's tankers.
concerning the article:
"Cooling Down Global Warming; 2011; UConn Today; Carbon capture has long been identified as a critical technology needed to prevent global warming, but efficient and economical ways to do it have been hard to find. A new process to capture and convert carbon dioxide, discovered by a UConn chemist in the College of Liberal Arts and Sciences, has just been awarded a patent. It uses cheap catalysts, electricity, and heat to convert CO2 and water into useful chemicals or fuels. Steve Suib, Board of Trustees Distinguished Professor of Chemistry and the 2011 Connecticut Medal of Science winner, found a way to use metal oxides, such as manganese and zinc oxides, as catalysts in a conversion process that also uses heat and electricity. (The) patents are jointly held by UConn, through the Office of Technology Commercialization, and Catelectric Advanced Electrocatalysis, a company that began as part of UConn’s Technology Incubation Program";
and, the patents:
"United States Patent 7,950,221 - Methods and Apparatus for Controlling Catalytic Processes; 2011; Inventor: Victor Stancovski; Assignee: Catalectric Corporation; Abstract: The present invention provides methods and apparatus for controlling catalytic processes, including catalyst regeneration and soot elimination“; and:
"United States Patent 7,964,084 - Methods and Apparatus for the Synthesis of Useful Compounds; 2011; Inventors: Victor Stancovski, Steven Suib, et. al.; Assignees: Catelectric Corporation and the University of Connecticut; Abstract: The present invention relates to methods and apparatus for activation of a low reactivity, non-polar chemical compound. In one example embodiment, the method comprises introducing the low reactivity chemical compound to a catalyst. At least one of (a) an oxidizing agent or a reducing agent and (b) a polar compound is provided to the catalyst and the chemical compound. An alternating current is applied to the catalyst to produce an activation reaction in the chemical compound. This activation reaction produces a useful product. (The) method ... wherein: the low reactivity chemical compound comprises CO2; and the useful product comprises at least one of ... ethane, ethylene, ... (or) at least one of an alcohol compound and an olefin";
scientists at the University of Connecticut and at UConn's technology spin-off, Catelectric Corporation, have devoted some considerable effort to studying, and have developed, a suite of technologies that would enable the efficient conversion of Carbon Dioxide - again as collected from whatever handy US source - into all sorts of hydrocarbon fuels and hydrocarbon chemicals, many of which could serve as raw materials in the further synthesis of plastics, wherein the CO2 consumed in their synthesis would be forever, and productively and profitably, sequestered.
Herein we submit to you yet another manifestation of UConn's Carbon Dioxide utilization technology, one which seems to be a culmination, or consolidation, of those we earlier reported; it is at least a more complete disclosure of the physical apparatus and chemical transformation steps involved in and needed for the transmutation of CO2 "lead" into hydrocarbon "gold"; and, one which reveals a surprising twist on how these transformational developments were actually financed and paid for.
And, since the intent of the technology being disclosed might not at first be perfectly clear from the rather dense technical dissertation, we submit to you the defining statement, as a foreword, as excerpted from section 11 of the official Summary:
"liquid hydrocarbon fuels can be generated directly from feedstocks containing only carbon dioxide and water".
Take it to the bank, they can be. As seen in more complete excerpts from the initial link in this dispatch, to:
"United States Patent Application 20120241327 - Materials and Design for an Electrocatalytic Device and Method which Produces Carbon Nanotubes and Hydrocarbon Transportation Fuels
Date: September 27, 2012
Inventors: Steven Suib, et. al.
Assignee: The University of Connecticut and Honda Motor Company, Tokyo
(Didn't see that one coming, did you? Well, considering the title with which we labeled this dispatch, maybe you did. Still surprising, though. However, as a search of the West Virginia Coal Association Research and Development archives would reveal, "Japan", in general, has an extensive documented history of alternative fuels development; and, we have in process multiple reports concerning the development, by Honda specifically, of efficient Hydrogen generation processes applicable to the general field of Carbon conversion and hydrogenation. Our take here is that Honda became aware of UConn's ongoing development of CO2 recycling technologies, and stepped in to provide what was some likely-needed financial support, as all of the named inventors would seem to be US citizens, or residents, and it doesn't appear as if Honda personnel participated directly in the technical development efforts.)
Abstract: The present teachings are directed toward an electrocatalytic cell including a barrier, having at least a first side and a second side opposite the first side, comprising a material permeable to oxygen ions and impermeable to at least CO2, CO, H2, H2O and hydrocarbons, an electrical power supply in communication with the barrier, a catalyst adjacent the first side of the barrier, a supply of feedstock components in communication with the first side of the barrier, a supply of a carrier gas component in communication with the second side of the barrier; wherein the feedstock components contact the catalyst and react to form hydrocarbon-containing components and oxygen-containing components, and the electrical power supply biases the barrier to thereby conduct oxygen ions from the first side to the second side. Also presented are a device and methods for producing carbon nanotubes.
(The "carbon nanotubes", as a co-product with "hydrocarbons", might not at first sound all that exciting. But, excreting Carbon, as it were, from the system, is directed toward the general goal of creating hydrocarbons from carbonaceous or hydrocarbonaceous compounds, wherein that goal is accomplished by either adding Hydrogen or subtracting Carbon, or both, as UConn and Honda seem to be doing herein, whichever is most economical and efficient. And, the "nanotubes" might, in fact, represent a profitable, or potentially profitable, product stream in and of themselves, which could serve to subsidize, as it were, the cost of making hydrocarbons from Carbon Dioxide. More about the rather surprising technical and market potentials for "carbon nanotubes" can be learned via:
Carbon nanotube - Wikipedia, the free encyclopedia; "Current use and application of nanotubes has mostly been limited to the use of bulk nanotubes, which is a mass of rather unorganized fragments of nanotubes. Bulk nanotube materials may never achieve a tensile strength similar to that of individual tubes, but such composites may, nevertheless, yield strengths sufficient for many applications. Bulk carbon nanotubes have already been used as composite fibers in polymers to improve the mechanical, thermal and electrical properties of the bulk product".
The "carbon nanotube" industry is still obviously in it's infancy; but, the full dissertation concerning nanotube structure and properties, and the full range of their potential uses and applications, is rather extraordinary. Having a ready source of them, like the CO2-recycling and hydrocarbon-synthesizing process disclosed herein by UConn and Honda, could open those now-potential markets up.)
Claims: An electrocatalytic method of producing carbon nanotubes, comprising providing an electrocatalytic reactor comprising a supported catalyst and a barrier comprising a material permeable to oxygen ions and impermeable to at least CO2, CO, H2, H2O and hydrocarbons; contacting working and counter electrodes to the supported catalyst; contacting the supported catalyst with a carbon-containing feedstock component and a hydrogen-containing feedstock component under electrocatalytic conditions sufficient to reduce the carbon-containing feedstock component; applying a voltage across the working and counter electrodes, and producing carbon nanotubes at the surface of the supported catalyst.
(Such "a material permeable to oxygen" is - or are, there are a number of possibilities - actually well-known in certain specialized industrial circles, and the concept falls into the area of "membrane separation" technology, more about which can be learned via:
And, there are companies who specialize in such things, as can be seen via:
a product information brochure, as it were, describing ceramic membrane technology developed by the Utah company, Ceramatec, who, as seen, for one example, in our report of:
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; 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";
have themselves figured our some intriguing ways to apply that membrane separation technology.)
The electrocatalytic method ... wherein the supported catalyst comprises at least one catalyst selected from the group consisting of Fe, Cu, Ni, Mn, V, Zn, Co, Fe/Co, alkali metal doped Fe/Co, alkali metal doped Co and mixtures thereof.
(Iron, Copper, Nickel, etc. Nothing too exotic, rare or expensive.)
The electrocatalytic method ... wherein the supported catalyst comprises a catalyst supported on at least one support selected from the group consisting of yttria-stabilized zirconia supports, reticulated vitreous carbon foam supports, reticulated fibrous silicon carbide supports, zinc oxide foam supports, boron carbide supports, alumina, zirconia, and carbon.
(Note in the above that "carbon foam supports" can be utilized for the catalyst, and we remind you of one of our reports concerning just where we might get such a semi-structural "carbon foam":
West Virginia Coal Association | Wheeling, WV, Coal-based Carbon Foam | Research & Development; concerning: "US Patent 6,656,238 - Coal-based Carbon Foam; 2003; Inventors: Darren Rogers and Janusz Wladyslaw, Wheeling and Glen Dale, WV; Assignee: Touchstone Research Lab, Triadelphia, WV".)
The electrocatalytic method ... wherein the carbon-containing feedstock component comprises at least one member selected from the group consisting of CO, CH4, C2H2, and C2H4.
The electrocatalytic method ... wherein the hydrogen-containing feedstock component comprises mixtures of H2 and H2O.
The electrocatalytic method ... wherein the contacting the supported catalyst with the carbon-containing feedstock component and a hydrogen-containing feedstock component occurs in an environment comprising 10% hydrogen.
An electrocatalytic cell comprising a barrier, having at least a first side and a second side opposite the first side, comprising a material permeable to oxygen ions and impermeable to at least CO2, CO, H2, H2O and hydrocarbons, an electrical power supply in communication with the barrier, a catalyst adjacent the first side of the barrier, a supply of feedstock components in communication with the first side of the barrier, a supply of a gas component in communication with the second side of the barrier; wherein the feedstock components contact the catalyst and react to form hydrocarbon-containing components and oxygen-containing components, and the electrical power supply biases the barrier to thereby conduct oxygen ions from the first side to the second side of the barrier.
The electrocatalytic cell ... further comprising an electrode in communication with the electrical power supply on the second side of the barrier.
The electrocatalytic cell ... wherein the feedstock component comprises mixtures of CO2 and CO with mixtures of H2 and H2O.
(Do note, that, as UConn and Honda emphasize in their formal Summary, the only raw materials really required by the process of this invention are "CO2" and "H2O". All the others mentioned, i.e., "CO", "H2", "CH4", "C2H2", and "C2H4", can be utilized, but, they aren't required or necessary.)
A method for producing hydrocarbons comprising, providing a hydrogen-containing feedstock component, providing a carbon-containing feedstock component, providing an electrocatalytic cell comprising a catalyst and a barrier comprising a material permeable to oxygen ions and impermeable to at least CO2, CO, H2, H2O and hydrocarbons, contacting the hydrogen-containing feedstock component with the carbon-containing feedstock component at the catalyst, producing hydrocarbon and oxygen ions at the catalyst, conducting oxygen ions across the barrier whereupon the oxygen ions release their electrons to an electrical circuit, and wherein at least one of the hydrogen-containing feedstock component and the carbon-containing feedstock component comprise oxygen-containing materials.
The method ... wherein the carbon-containing feedstock component comprises mixtures of CO2 and CO.
(They keep specifying "CO", Carbon Monoxide", as desirable in mixture with the "CO2", Carbon Dioxide. And, if some Carbon Monoxide is, in fact advantageous, in addition to CO2, then, as seen 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";
using very efficient electrocatalytic techniques closely related to those of our subject, "United States Patent Application 20120241327", we can make any Carbon Monoxide that might be needed or desirable out of Carbon Dioxide.)
The method ... wherein the hydrogen-containing feedstock component comprises mixtures of H2 and H2O.
(In a similar way, UConn and Honda specify that some Hydrogen might be desirable in addition to Water; and, if so, then, again in a similar way, as seen for one example in our report of:
West Virginia Coal Association | Germany Makes Economical Hydrogen from H2O | Research & Development; concerning: "United States Patent Application 20090026089 - System and Method for Splitting Water; 2009; Assignee: Hermsdorfer Institut, Germany; Abstract: The present invention relates to a system and a method for cleaving water by means of hyperpolarisation, the system comprising a first electrode and at least one additional electrode; at least one porous ferroelectric layer arranged between the first and the additional electrode; as well as an AC voltage or pulsed DC voltage source. With the method according to the present invention it is possible to cleave the water economically into hydrogen and oxygen and obtain gases for technical purposes";
efficient electrochemical and electrocatalytic processes exist as well to extract Hydrogen from Water. And, in point of fact, as we will document in a few reports to follow, that is an area of technology that UConn's partner, Honda, devoted themselves separately to; and, that might be one reason the two entities chose to collaborate in the formulation of the electrochemical Carbon Dioxide-recycling, hydrocarbon-synthesizing process disclosed herein.)
The method ... further comprising removing the hydrocarbons produced from the hydrogen-containing feedstock component and the carbon-containing feedstock component at the catalyst from the electrocatalytic cell.
The method ... further comprising providing a reductant-containing component, and reacting the reductant-containing component with the oxygen ions after they release their electrons to an electrical circuit (and) wherein the reductant-containing component comprises at least one member selected from the group consisting of hydrogen, ammonia, and hydrazine.
(The above is a further note of complexity that might or might not be needed, although it could provide some energy to help drive the process. Ammonia, especially, can be obtained rather inexpensively as the byproduct of other chemical processes.)
Background and Field: The present teachings are directed to methods of producing carbon nanotubes and hydrocarbons, especially fuels for transportation, and to electrocatalytic cells for performing the methods disclosed herein.
Various methods of preparing carbon nanotubes are well known, for instance, laser ablation, arc discharge, and chemical vapor deposition. Each of these methods has various shortcomings unique to the method.
Gasification of a carbonaceous source material followed by water gas shift and Fischer-Tropsch chemistry is one commercial method to produce hydrocarbons from the feeds of CO, CO2, H2 and H2O. Fischer-Tropsch ("FT") chemistry typically relies on a syngas feedstock, which is a mixture of carbon monoxide and dihydrogen (H2) in an explicitly defined ratio. Typically, feedstocks must contain hydrogen in order for FT chemistry to occur. The difficulties associated with storing and transporting both hydrogen and carbon monoxide result in the carbonaceous source material being gasified in relatively close proximity to a FT plant.
(The "carbonaceous source material" would, of course, be Coal.)
The ability to use as feedstock sources variably composed mixtures of CO2/CO with variable composed mixtures of H2/H2O for the FT synthesis for liquid hydrocarbon transportation fuels is greatly desirable.
(The process could, in fact, be seen as one way to process synthesis gas derived from Coal into hydrocarbons, as an alternative to the Fischer-Tropsch, or related, synthesis. But, this really is all about the conversion of CO2 and H2O, and/or CO and H2, into hydrocarbons, no matter where we get them.)
Summary: The present disclosure is directed to an electrocatalytic method of producing carbon nanotubes by providing an electrocatalytic reactor including a supported catalyst and a barrier comprising a material permeable to oxygen ions and impermeable to at least CO2, CO, H2, H.2O and hydrocarbons. There are working and counter electrodes contacted to the supported catalyst. The supported catalyst is then contacted with a carbon-containing feedstock component and a hydrogen-containing feedstock component under electrocatalytic conditions sufficient to reduce the carbon-containing feedstock component, a voltage is applied across the working and counter electrodes, and carbon nanotubes are produced at the surface of the supported catalyst.
The present teachings are also directed to (an) electrocatalytic cell including a barrier which has a first side and a second side opposite the first side, and is composed of a material permeable to oxygen ions and impermeable to at least CO2, CO, H2, H2O and hydrocarbons. The electrocatalytic cell further includes an electrical power supply in communication with the barrier, a catalyst adjacent the first side of the barrier, a supply of feedstock components in communication with the first side of the barrier, and a supply of a carrier gas component in communication with the second side of the barrier. The feedstock components contact the catalyst and react to form hydrocarbon-containing components and oxygen-containing components, and the electrical power supply biases the barrier to thereby conduct oxygen ions from the first side to the second side, while the hydrocarbon-containing components are collected.
Also taught by the present disclosure is a method for producing hydrocarbons by providing a hydrogen-containing feedstock component and a carbon-containing feedstock component. It is further taught that at least one of the hydrogen-containing feedstock component and the carbon-containing feedstock component comprise oxygen-containing materials. Also taught is an electrocatalytic cell including a catalyst and a barrier made up of a material permeable to oxygen ions and impermeable to at least CO2, CO, H2, H2O and hydrocarbons. The hydrogen-containing feedstock component and the carbon-containing feedstock component are contacted with one another at the catalyst thereby producing a hydrocarbon component and oxygen ions at the catalyst. The oxygen ions are conducted across the barrier, releasing their electrons to an electrical circuit, and forming dioxygen molecules which are removed from the electrocatalytic cell. The hydrocarbon component is also removed from the electrocatalytic cell.
The presently disclosed method can utilize thermo-catalytic and electro-catalytic materials which vastly expand the nature of precursors or sources which can be used to produce liquid hydrocarbon transportation fuels. Specifically, variably composed mixtures of CO2/CO with variable composed mixtures of H2/H2O can be used as feedstock materials for liquid hydrocarbon transportation fuels.
With the presently disclosed method, liquid hydrocarbon fuels can be generated directly from feedstocks containing only carbon dioxide and water.
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We'll close our over-long excerpts there, since the above statement is the distilled essence of the thing:
Despite all the specifications concerning mixtures of Carbon Monoxide and Carbon Dioxide, and of Hydrogen and Water, all that's really needed by the process of this invention to make "hydrocarbons" is "carbon dioxide and water".
They go on to specify in additional explication that "solar, wind, and mechanical wave energy are possible energy sources to input into the present method as energetic sources".
We've already separately documented many times how all of those can be applied to various processes of Carbon conversion, whether the starting raw material is Coal or CO2, and don't want to clutter our over-long presentation herein with yet more references. We will address them all again in additional future reports.
The point, in sum, according to the University of Connecticut and Honda Motors, is this:
Starting only with "carbon dioxide and water", and using only available environmental energy, we can synthesize both industrially-valuable "carbon nanotubes" and "liquid hydrocarbon fuels".
When do we start
