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USDOE Pays for Illinois 2015 CO2 to Methane and Alcohol

United States Patent: 9012345

Carbon Dioxide, as is co-produced 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 - by our economically essential use of Coal in the generation of abundant, reliable and affordable electric power, can be seen and treated as a valuable raw material resource.

As seen for just one example in our recent 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. ... 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 fact that Carbon Dioxide, as harvested from whatever convenient source, can be efficiently consumed in the synthesis of "fuels and chemicals" was acknowledged in one case by the United States Department of Energy, through their support of research and development work focused on such productive utilization of Carbon Dioxide undertaken by the University of Illinois at Urbana-Champaign.

As noted in that report, we have made other reports noting the exemplary work being performed at the University of Illinois, UI, in programs of research and study overseen by professors Rich Masel and Paul Kenis; but, our own personal insufficiencies prevent us from documenting those past reports. However, we did, we are certain, make note of the fact that the UI CO2 utilization developments led to the founding of a company, "Dioxide Materials, Incorporated", focused on the further development and commercialization of UI's Carbon Dioxide recycling achievements.

And, herein we learn, that, just two weeks ago, our United States Government officially confirmed that Rich Masel, and a colleague, and Dioxide Materials, in further execution of the above-noted US Department of Energy Grant SC0004453 awarded to the University of Illinois at Urbana-Champaign, have succeeded in developing a catalyst and related technology that enables the efficient use and consumption of Carbon Dioxide, as harvested from whatever source, into a variety of products, including substitute natural shale gas Methane and fuel alcohol Ethanol.

As seen in excerpts from the initial link in this dispatch to:

"United States Patent 9,012,345 - Electrocatalysts for Carbon Dioxide Conversion

Electrocatalysts for carbon dioxide conversion - Dioxide Materials, Inc.

April 21, 2015

Inventors: Richard Masel and Amin Salehi-Khojin

Assignee: Dioxide Materials, Inc., Champaign, Illinois

(Dioxide Materials | Research Park; "Dioxide Materials Inc. is a startup based in Champaign IL that is developing products for CO2 sensing and CO2 utilization based on a patent pending catalyst that allows CO2 conversion to occur at record selectivity and energy efficiency (more than 97% selectivity and more than 80% overall energy efficiency). Our long term goal is to create a new chemical value chain using carbon dioxide feedstock and renewable energy (instead of oil and gas) to obtain high value fuels and chemicals".

Dioxide Materials Inc. | Office of Technology Management, Urbana-Champaign; "Dioxide Materials develops and licenses new technology for CO2 remediation. This includes technology to reduce the amount of CO2 that is produced, and technology to create uses for any CO2 that is formed. The company is focused on devices that reduce the carbon footprint of homes and businesses and processes that convert waste CO2 into useful fuels and chemicals. The company aims to make homes and businesses safer and more energy efficient and to reduce the carbon footprint of US industry. Founded by Dr. Rich Masel, Dioxide Materials is located in the University of Illinois Research Park".

Dioxide Materials- Technology to lower the carbon footprint of homes and businesses; "Dioxide Materials develops technology that saves people money, helps the environment, and lowers US dependence on imported oil. We have ... technology in two areas: Carbon dioxide sensors (and) Processes that convert carbon dioxide produced by homes and businesses back to fuels and chemicals (thus) creating a viable source of renewable fuels and a viable energy storage method for wind farms.") 

Abstract: Electrocatalysts for carbon dioxide conversion include at least one catalytically active element with a particle size above 0.6 nanometer. The electrocatalysts can also include a Helper Catalyst. The catalysts can be used to increase the rate, modify the selectivity or lower the overpotential of electrochemical conversion of CO2. Chemical processes and devices using the catalysts also include processes to produce CO (carbon monoxide), ... CH4 (methane), ... CH3CH2OH (ethanol), (and other products), and a specific device, namely, a CO2 sensor.

Government Interests: This invention was made, at least in part, with U.S. government support under U.S. Department of Energy Grant DE-SC0004453. The government has certain rights in the invention.

Claims:  An electrocatalyst comprising at least one catalytically active element, wherein: said catalytically active element is in the form of particles supported on an electrically conductive support or unsupported particles, the particles of the at least one catalytically active element have an average size (as specified), the at least one catalytically active element is in electrical contact with an electrode of an electrochemical cell or device, and the electrocatalyst is capable of converting CO2 to a carbon-containing reaction product. 

The electrocatalyst ... further comprising a Helper Catalyst. 

(The above, somewhat ambiguous "Helper Catalyst" will be further disclosed and more fully explained in reports of Dioxide Materials technology to follow, and in further Claims herein.)

The electrocatalyst ... wherein said catalytically active element comprises at least one of Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper, (and other metals specified - including Silver, which seems to be preferred). 

The electrocatalyst ... wherein said products comprise at least one of the following: (Carbon Monoxide), (Methane), (Ethanol), (and others).

(Dioxide Materials provide formulae for the products that can be made from Carbon Dioxide via the process of our subject, "United States Patent 9,012,345 - Electrocatalysts for Carbon Dioxide Conversion". We selected the ones above for specific mention only because of the further potentials for them we know of to exist. For a perhaps surprising example, for instance, as seen in our report of: 

Standard Oil Carbon Monoxide + Water = Gasoline | Research & Development | News; concerning: "United States Patent 4,559,363 - Process for Reacting Carbon Monoxide and Water; 1985; Inventors: Jeffrey Miller and Albert Hensley; Abstract: A process for reacting carbon monoxide and water in the presence of a cadmium-containing catalyst is disclosed. A method for the production of hydrocarbons by reacting carbon monoxide and water ... . This invention relates generally to the reaction between carbon monoxide and water, and more particularly concerns such reaction in the presence of a cadmium-containing catalyst. It is a general object of the present invention to provide a method for the direct production of gasoline";

the product Carbon Monoxide can be used rather directly for the synthesis of Gasoline.

The electrocatalyst ... wherein said catalytically active element comprises silver (and) wherein said Helper Catalyst comprises at least one of  ... phosphines, imidazoliums, pyridiniums, pyrrolidiniums, phosphoniums, sulfoniums, prolinates, and methioninates. 

The electrocatalyst ... wherein said Helper Catalyst comprises cholines (and other compounds, as specified). 

The electrocatalyst ...  wherein said Helper Catalyst is one of a solvent, an electrolyte and an additive.

Background and Field: The field of the invention is catalysis and catalysts. The catalysts of this invention are applicable, for example, to the electrochemical conversion of carbon dioxide into useful products. ... Over the years, a number of electrochemical processes have been suggested for the conversion of CO2 into useful products.

(Dioxide Materials goes on to name and specify some of those prior "electrochemical processes (which) have been suggested for the conversion of CO2 into useful products". Among their examples are a number about which we have previously reported, such as, for several examples:

USDOE 1976 Atmospheric CO2 to Methanol | Research & Development | News; 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"; and:

Chicago Recycles CO2 to Methane | Research & Development | News; concerning: "United States Patent 4,609,440 - Electrochemical Synthesis of Methane; 1986; Inventor: Karl Frese, et. al., CA; Assignee: Gas Research Institute, Chicago; Abstract: A method is described for electrochemically reducing carbon dioxide to form methane by electrolyzing an aqueous solution containing carbon dioxide"; and:

Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development | News; concerning: "United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes; 1987; Assignee: The Standard Oil Company, Cleveland; 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".)

When an electrochemical cell is used as a CO2 conversion system, a reactant comprising CO2, carbonate or bicarbonate is fed into the cell. A voltage is applied to the cell, and the CO2 reacts to form new chemical compounds.

Summary: The invention provides a novel catalyst mixture that can overcome one or more of the limitations of low rates, high overpotentials and low ... efficiencies (of prior Carbon Dioxide electrochemical utilization and conversion technologies)".


The full Disclosure, in point of fact, contains further discussion of how the specified "Electrocatalysts" of "United States Patent 9,012,345" can be used to help facilitate other chemical reactions, as well, in addition to those that result in "Carbon Dioxide Conversion" into, for example, substitute shale natural gas Methane, thus eliminating the need for worrisome fracking, and fuel alcohol Ethanol, thus eliminating the need to consume, via fermentation, increasingly valuable products of agriculture - which could find far better use as food - in the production of that liquid fuel.

As in Dioxide Materials' public statements, reproduced in our inserted comments above, "United States Patent 9,012,345 - Electrocatalysts for Carbon Dioxide Conversion", and other Dioxide Materials technologies about which we will be reporting, enable us to use "carbon dioxide feedstock and renewable energy ... to obtain high value fuels and chemicals".

And, through "U.S. Department of Energy Grant DE-SC0004453", tax money collected from all of us United States citizens was used to help pay for the development of the technology and processes embodied in "United States Patent 9,012,345 - Electrocatalysts for Carbon Dioxide Conversion", which likely enable us to use just low grade "renewable energy", as specified elsewhere by Dioxide Materials, to convert Carbon Dioxide into, among other things, fuel alcohol and substitute natural gas Methane.

All we US citizens, thus, through our government, own a share of "US Patent 9,012,345 - Electrocatalysts for Carbon Dioxide Conversion".

Time we were all told about it, don't you think, before blatant Carbon Dioxide-based exploitations - - like Cap and Trade taxation, and/or the geologic sequestration of Carbon Dioxide, to be performed at the expense of consumers of Coal-based electric power, but which practice, through secondary oil recovery in nearly-depleted natural petroleum reservoirs proposed for use as CO2 sequestration sites, increases the profits of the oil industry - - lurch one step further towards being established as law?