United States Patent Application: 0140093799

Carbon Dioxide - - as it is co-produced in a small way, relative to some all-natural and un-taxable sources of its global emission, such as the Earth's inexorable processes of planetary volcanism, by our economically essential use of Coal in the generation of reliable, abundant and affordable electric power - - is a valuable raw material resource.

We can reclaim Carbon Dioxide from whatever source might be most convenient to us, even the atmosphere itself, and then convert, recycle, that Carbon Dioxide via efficient processes into any and all forms of valuable hydrocarbons, including both gaseous and liquid hydrocarbon fuels.


We've previously documented the Carbon Dioxide-recycling work of University of Illinois professor Dr. Richard Masel, and of his graduate student, Wei Zhu, as in our report of:

USDOE Hires Illinois to Recycle CO2 into Fuels | Research & Development | News; concerning: "Amine Promotion Of Hydrogen Evolution Reaction Suppression And CO2 Conversion For Artificial Photosynthesis; Wei Zhu; Dissertation: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemical Engineering in the Graduate College of the University of Illinois at Urbana-Champaign, 2011; Doctoral Committee: Professor Richard I. Masel, Professor Paul Kenis, et. al. Recycling CO2 back into fuels or other useful products is critically important (and, the) electrochemical method is regarded as a promising means to do this because it has the advantage that water can be used as the proton source. ... Choline based products are chosen as ideal electrolytes to achieve both hydrogen evolution reaction suppression and lowering of CO2 reduction overpotential ... . Based on the experimental data, we have discovered that if we conduct CO2 reduction in choline based quaternary ammonium salts, the overpotential decreases and the starting potential of hydrogen evolution increases. ... Artificial photosynthetic systems offer the possibility of producing fuels and chemicals from CO2 and sunlight in fewer steps and with higher efficiencies than is possible in natural photosynthesis. ... This work was supported by the US Department of Energy under grant DE-SC0004453. ... The long term goal of our research is to develop better electrochemical systems for CO2 reduction in room-temperature electrolyte that could lead to efficient processes for the large-scale conversion of CO2 into formic acid or other products. ... The objective of our work is to learn how to use artificial electrochemical synthesis to create materials for renewable fuels. Specifically, we will be examining the mechanism of CO2 conversion on different catalysts ... This work was supported by the US Department of Energy under grant DE-SC0004453".

We'll be returning to the above "US Department of Energy under grant DE-SC0004453", and the Carbon Dioxide utilization technology developed through the research work supported by it, in future reports. We're jumping ahead here a bit, though, to make report of immediate developments involving the work being done by Masel and Zhu in the conversion of Carbon Dioxide into, among other things, "synthetic fuels".

To that end, we also remind you of Carbon Dioxide recycling and reuse research work undertaken one half of one century ago by our United States Air Force, as, for example, in our reports of:

US Air Force 1965 CO2 to Fuel Conversion | Research & Development | News; concerning: "'Catalytic Reduction of Carbon Dioxide to Methane and Water'; This report sunmarizes the work accomplished under contract AF 3"(615)-1210, for research on catalytic reduction of carbon dioxide to methane and water This work was performed under project 6146, "Atmosphere and Thermal Control",- and task 614622, "Oxygen Recovery From Carbon Dioxide." The effort was initiated on 6 January 1964 and completed 31 December 1964, by the NRD Division of the General American Transportation Corporation, ... Niles, Illinois 60648. The work was monitored by Lt. Derry W. Marshall, Environmental Control Branch (FDFE), Air Force Flight Dynamics Laboratory, Research and Technology Division, Wright-Patterson Air Force Base, Ohio"; and:

More US Air Force 1965 CO2 Recycling | Research & Development | News; concerning: "'Investigation of Catalytic Reactions for CO2 Reduction; Part II'; Technical Documentary Report No. FDL-TDR 64-22: April, 1965; Edward Thompson; Air Force Flight Dynamics Laboratory; Wright-Patterson AFB, Ohio; Abstract: Several base metal and base metal oxide CO2 reduction catalysts were selected for investigation
as Part II of an in-house research program to determine catalytic effectiveness in promoting the reduction of carbon dioxide by hydrogen to methane and water".

And, herein we learn that our United States Air Force sponsored on-going, much more recent efforts, by Richard Masel and Wei Zhu, and another of their colleagues, to develop processes whereby Carbon Dioxide could be even more efficiently converted into what seems a full range of hydrocarbon products, including, perhaps most intriguingly at this point in our national history, "synthetic fuels".

As seen in excerpts from the initial link in this dispatch, as published just yesterday, to:

"United States Patent Application 20140093799 - Devices and Processes for Carbon Dioxide Conversion into Useful Fuels and Chemicals

Devices And Processes For Carbon Dioxide Conversion Into Useful Fuels And Chemicals - Masel, Richard I.

Date: April 3, 2014

Inventors: Richard Masel, IL, Brian Rosen, DE, Wei Zhu, IL

(Professor Rich Masel's Website)

Applicant (and presumed eventual Assignee of rights): Dioxide Materials, Inc., Champaign, IL

(We'll have more on "Dioxide Materials", founded by Dr. Masel, in reports to follow, although we believe we have mentioned them once or twice previously. For now, more can be learned via:

Dioxide Materials- Technology to lower the carbon footprint of homes and businesses; "Energy Efficient CO2 Recycling to High Value Fuels and Chemicals; Dioxide Materials is creating a new chemical value chain using Carbon Dioxide (instead of oil and gas) as a feedstock for the synthesis of high value fuels and chemicals. ... The goal is to create a new industry where waste carbon dioxide from power plants is used as a feedstock to produce gasoline, diesel fuel, jet fuel and industrial chemicals".)

Abstract: Electrochemical devices for converting carbon dioxide to useful reaction products include a solid or a liquid with a specific pH and/or water content. Chemical processes using the devices are also disclosed, including processes to produce CO, ... CH3OH (Methanol), CH4 (Methane), ... acrylic acid, diphenyl carbonate, other carbonates, other organic acids and synthetic fuels.

The electrochemical device can be a CO2 sensor.

(There are separate disclosures of, as above, "CO2 sensor"s. We haven't treated them separately since they don't pertain directly to one of our core theses, the productive utilization of Carbon Dioxide. Further, the Abstract lists and identifies other compounds which can be synthesized from Carbon Dioxide, but does so only by chemical formula which are beyond our meager abilities to translate for you.)

Government Interests: This invention was made, at least in part, with U.S. government support under U.S. Air Force contract No. FA8650-12-M-2249. The government has certain rights in the invention.

Claims: An electrochemical device for converting CO2 to a reaction product, the electrochemical device comprising a cathode and a component located within 1 millimeter of the cathode, the component comprising at least one of: (a) an electrolyte; (b) a Helper Catalyst; (c) a solution; (d) a liquid; (e) a Functional Unit; and (f) a solid, wherein the component comprises a substance having a pH (as specifed).

The electrochemical device ... wherein at least one of the electrolyte, liquid, solid or solution has a concentration (as specified, and) further comprising a membrane electrode assembly, the membrane electrode assembly comprising: (i) a cathode; (ii) a cathode catalyst; (iii) a Buffer Layer; (iv) a separator membrane; (v) an anode catalyst; and (vi) an anode (and) wherein the Buffer Layer is located within 1 mm of the cathode, the Buffer Layer comprising a substance having a pH of 1.1-5.5 ... .

(The "Helper Catalyst" and "Buffer Layer" themselves are specific and proprietary components of this technology, which have their own formal disclosures and descriptions, and which we might eventually treat more fully in reports to follow. The labels are capitalized to emphasize that they are known  established and identified. Supporting documentation more fully described them.)

The electrochemical device ... wherein at least one of the cathode and a catalyst operatively associated with the cathode comprises a catalytically active element (and)wherein the catalytically active element comprises at least one of Vanadium, ...Manganese, Iron, Cobalt, Nickel, Copper (and, etc.) ad wherein the catalytically activeelement comprises at least one of Platinum, Palladium, Gold, Silver, Copper (and etc.),and (more specifically)wherein the catalytically active element comprises Silver.

The electrochemical device ... wherein the Helper Catalyst comprises at least one of a phosphine, an imidazolium, a pyridinium, a pyrrolidinium, a phosphonium, a sulfonium, a prolinate, a methioninate and a choline (and) wherein the choline comprises one of a choline salt and a choline ester salt.

The electrochemical device ... wherein the reaction product comprises at least one of (Carbon Monoxide), (Formic Acid), (Methanol), (Methane), (and, etc.).

A process for making a reaction product, comprising introducing at least one of CO2, a carbonate and a bicarbonate to the cathode of the electrochemical device ... and applying electrical energy to the electrochemical device to effect electrochemical conversion of the at least one of CO2, a carbonate and a bicarbonate to the reaction product.

Background and Field: The field of the invention is electrochemistry. The devices and systems of this invention are applicable, for example, to the electrochemical conversion of carbon dioxide into useful products. 

Summary:An electrochemical device converts CO2 into other chemical reaction products."


Again, among the "useful products" which can be synthesized via the process of our subject, "United States Patent Application 20140093799 - Devices and Processes for Carbon Dioxide Conversion into Useful Fuels and Chemicals", from Carbon Dioxide, are, as specified, Methane and Methanol.

And, we remind you, that, as seen in our report of:

California 2013 CO2 + Methane = Methanol | Research & Development | News; concerning: "United States Patent 8,440,729 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane; Date: May 14, 2013; Inventors: George Olah and G.K. Surya Prakash, CA; Assignee: University of Southern California, Los Angeles; Abstract: The invention provides for a method of forming methanol by combining a mixture of methane, water and carbon dioxide under specific reaction conditions sufficient to form a mixture of hydrogen and carbon monoxide which are then reacted under conditions sufficient to form methanol";

once we have Methane, as synthesized via the process herein of "United States Patent Application 20140093799" from Carbon Dioxide, we can then react that CO2-based Methane with even more Carbon Dioxide, and thereby make even more Methanol, as is also synthesized via the process of "United States Patent Application 20140093799" from Carbon Dioxide.

Further, as seen in our report of:

ExxonMobil Coal to Methanol to Gasoline | Research & Development | News; concerning both: "United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification; 1982; Assignee: Exxon Research and Engineering Company; Abstract: Methanol is produced by gasifying a carbonaceous feed material with steam (and) wherein said carbonaceous feed material comprises coal"; and: "United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation; This invention relates to the method and system for converting methanol to gasoline";

once we have so much Methanol, as synthesized from one or the other of our abundant Carbon resources, whether Coal or Carbon Dioxide, we can then convert that Methanol directly into some of the stuff we have seemed so willing to fight Persian Gulf wars and spend our nation into the poorhouse to continue buying from all of those bastions of freedom and liberty and democracy allied together in that beneficent brotherhood of nations known as OPEC.

As admirable as our unswerving willingness to so lavishly support that peace-loving and charitable league has been, maybe it's time we started to think a little bit about the economic, environmental and political futures of our children and grandchildren here in United States Coal Country, heck, to be big about it, in the entire United States of America. 

That sounds inexcusably selfish, we know - which might be one reason the deacons of our Coal Country press have so far kept their lips so tightly pursed about the now irrefutable facts that we can efficiently convert both our abundant Coal and our, some say, too abundant Carbon Dioxide into such things - - as stipulated herein by our subject, "United States Patent Application 20140093799 - Devices and Processes for Carbon Dioxide Conversion into Useful Fuels"; the development of which was paid for with our tax dollars, and which, through the United States Air Force, We the People own a share of - - as fuel alcohol Methanol and substitute natural gas Methane.

In any case, Professor Masel and Dioxide Materials have other technologies in the works, related to the conversion of Carbon Dioxide into "synthetic fuels", as well, which we will in the fullness of time be reporting to you. And, the reports of those technologies all will serve as further proof of one now seemingly incontrovertible fact: 

Carbon Dioxide - - as it is co-produced in a small way, relative to some all-natural and un-taxable sources of its global emission, such as the Earth's inexorable processes of planetary volcanism, by our economically essential use of Coal in the generation of reliable, abundant and affordable electric power - - is a valuable raw material resource.

West Virginia Coal Association - PO Box 3923 - Charleston, WV 25339 | 304-342-4153 | website developed by brickswithoutstraw