United States Patent: 8663447

We first remind you of our many reports concerning the US Government-sponsored work undertaken in the Princeton University labs of Professor Andrew Bocarsly, as, for one example, seen in:

Princeton University November 20, 2012 CO2 to Ethanol | Research & Development | News; concerning:

"United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products; November 20, 2012;

Inventors: Andrew Bocarsly and Emily Barton Cole; Assignee: Princeton University, NJ; Abstract: The invention relates to various embodiments of an environmentally beneficial method for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in a divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor cathode electrode in another cell compartment that also contains an aqueous solution of an electrolyte and a catalyst of one or more substituted or unsubstituted aromatic amines to produce therein a reduced organic product. Government Interests: This invention was made with United States government support from National Science Foundation Grant No. CHE-0616475. The United States Government has certain rights in this invention. Claims: A method of converting carbon dioxide to provide at least one product selected from the group consisting of glyoxal, isopropanol, ethanol ... and mixtures thereof";

wherein it was seen that we can, indeed, treat Carbon Dioxide - - as might be co-produced during our economically essential use of Coal in the generation of truly abundant and truly affordable electric power - -  as a valuable raw material resource from which we can synthesize such seemingly-needful things as fuel alcohol "ethanol".

And, we note again that such Government-sponsored CO2-utilization development work is continuing, as in for example our report of:

The USDOE and New Jersey Convert CO2 into Ethanol | Research & Development | News; concerning: "United States Patent Application 20130199937 - Reducing Carbon Dioxide to Products; August 8, 2013; Inventors: Emily Barton Cole, et. al., Texas and New Jersey; Assignee: Liquid Light, Inc., NJ; Abstract: A method reducing carbon dioxide to one or more products ... . Government Interests: This invention was made with government support under Grant DE-SC0006201 awarded by the Department of Energy. The government has certain rights in the invention. A method for reducing carbon dioxide to one or more products ... wherein said products comprise one or more of ... ethane, ethanol, ethylene";

in a company, "Liquid Light", which has been described as a "spin-off" from Princeton University; one intended to further develop and to commercialize the Carbon Dioxide utilization technologies initially established in Princeton's Bocarsly lab.

And, herein we see that our United States Government recently affirmed that even additional Carbon Dioxide utilization technology developed at Princeton University, in work funded by the United States Government, is, in fact, viable and practicable.

Comment follows excerpts from the initial link in this dispatch to:

"United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products

(Note that Princeton, Bocarsly, et. al., have a significant number of United States Patents issued and Patent Applications "on the books", with some of them bearing similar titles. The key to their differentiation lies in the specific "Organic Products" which are being produced via the "Conversion of Carbon Dioxide".)

Patent US8663447 - Conversion of carbon dioxide to organic products - Google Patents

Conversion of carbon dioxide to organic products - Princeton University

Date: March 4, 2014

Inventors: Andrew Bocarsly, NJ, and Emily Barton Cole, TX

Assignee: Princeton University, NJ

Abstract: The invention relates to various embodiments of an environmentally beneficial method for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in a divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor cathode electrode in another cell compartment that also contains an aqueous solution of an electrolyte and a catalyst of one or more substituted or unsubstituted aromatic amines to produce therein a reduced organic product.

Government Interests: This invention was made with United States government support from National Science Foundation Grant No. CHE-0616475.

The United States Government has certain rights in this invention.

(The above is the same grant which funded development of the CO2-recycling process disclosed in our prior report concerning Princeton's "United States Patent 8,313,634".)

Claims: An environmentally beneficial method of producing methanol by electrochemical reduction of any available source of carbon dioxide, which comprises: providing a divided electrochemical cell comprising an anode in a first cell compartment and a cathode in a second cell compartment that also contains a catalyst which is one or more of a substituted or unsubstituted aromatic heterocyclic amine selected from the group consisting of a pyrazine, a pyridazine, and a pyrimidine, both compartments containing an aqueous solution of an electrolyte; providing carbon dioxide from an existing source into the second cell compartment; and electrochemically reducing the carbon dioxide in the second cell compartment to produce methanol.

(The above is the one and only "Claim" made for the process disclosed by this patent, it's sole purpose being to electrochemically convert Carbon Dioxide and water, "an aqueous solution", into the versatile fuel alcohol, "methanol". And, we remind you of other, similar, technology about which we've reported, which is, in fact, cited by Bocarsly and Cole as "precedent art"; as in our report of: 

California Recycles More and More Carbon Dioxide | Research & Development | News; which includes documentation of, among others related, as specifically cited by our subject herein:"United States Patent 7,704,369 - Electrolysis of Carbon Dioxide ... for Production of Methanol; 2010; Inventors: George Olah and Surya Prakash; Assignee: University of Southern California, Los Angeles; Abstract: An environmentally beneficial method of producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning power plants".)

Description:Various options for carbon dioxide reduction have been proposed. In addition to energy conservation, carbon capture and storage, the process of separating CO2 from emission sources and transporting it to a storage location for long-term (indefinite) isolation, and carbon sequestration, the process of permanently storing CO2 underground, have garnered the most attention to date.

However, these technologies face significant challenges and are presently far from being cost effective.

In addition, sequestration has raised serious environmental concern, legal and regulatory issues due to the unknown ramifications of permanently storing CO2 underground. 

In accordance with embodiments of the invention, an electrocatalytic system is provided that allows carbon dioxide to be converted at very modest overpotentials to highly reduced species in aqueous solution, in other words, carbon-carbon and/or carbon-hydrogen bonds are formed in aqueous solution under very mild condition utilizing a minimum of energy.

In some embodiments, the required energy input may be generated from an alternative energy source or directly using visible light depending on how the system is implemented. 

In embodiments of the invention, the reduction of carbon dioxide is suitably catalyzed by aromatic heterocyclic amines, e.g., pyridinium, imidazole and their substituted derivatives. These simple organic compounds have been found to be effective and stable homogenous electrocatalysts and photoelectrocatalysts for the aqueous multiple electron, multiple proton reduction of carbon dioxide to organic products such as ... methanol. For production of methanol, the reduction of carbon dioxide proceeds along (a specified reaction) pathway. High faradaic yields for the reduced products have been found in both electrochemical and photoelectrochemical systems at low reaction overpotentials. 

It has previously been thought that metal-derived multi-electron transfer was necessary to achieve highly reduced products such as methanol. Surprisingly, the simple aromatic heterocyclic amine molecules in accordance with embodiments of the invention are capable of producing many different chemical species on route to methanol through multiple electron transfers instead of metal-based multi-electron transfer. 

The invention thus relates to various embodiments of environmentally beneficial methods for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in an aqueous, electrolyte-supported divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor working cathode electrode in another cell compartment that contains a catalyst of one or more substituted or unsubstituted aromatic heterocyclic amines to produce a reduced organic product. CO2 is continuously bubbled through the cathode electrolyte solution to saturate the solution. 

(Various electrode materials and catalysts are identified and specified and identified. Further, a number of intermediate products which can be withdrawn from the reaction sequence, on the way from Carbon Dioxide to the end product Methanol, are also identified.)

The effective electrochemical/photoelectrochemical reduction of carbon dioxide disclosed herein provides new methods of producing methanol and other related products in an improved, efficient, and environmentally beneficial way ... . Moreover, the methanol product of reduction of carbon dioxide can be advantageously used as (1) a convenient energy storage medium, which allows convenient and safe storage and handling; (2) a readily transported and dispensed fuel, including for methanol fuel cells; and (3) a feedstock for synthetic hydrocarbons and (other) products currently obtained from oil and gas resources, including polymers, biopolymers and even proteins, which can be used for animal feed or human consumption. Importantly, the use of methanol as an energy storage and transportation material eliminates many difficulties of using hydrogen for such purposes. The safety and versatility of methanol makes the disclosed reduction of carbon dioxide further desirable."

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Concerning the above suggested use of "methanol", as efficiently made herein from Carbon Dioxide, as "a feedstock for synthetic hydrocarbons", we remind you, that, 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 ... wherein said carbonaceous feed material comprises coal"; and: "United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation; Abstract: The conversion of methanol to gasoline ... in a plurality of sequentially arranged catalyst beds";

no matter which of abundant and precious natural resources we make it from, whether Coal or Carbon Dioxide, Methanol, once we have it, can be directly and efficiently converted into the "hydrocarbons" we seem content now to squander our grandchildren's inheritance to keep buying from our "friends" in OPEC.

The full Disclosure of our subject, the quite recently-awarded "United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products", goes into some considerable detail about the process efficiencies, and about how those efficiencies enable the whole process of converting Carbon Dioxide, as recovered from whatever handy source, into Methanol to be driven by, for instance, low-level photovoltaic electricity, and, unless we misread it, even almost directly, by light energy itself, which would qualify this, we suppose, as another in a string of "artificial photosynthesis" technologies which have been developed around the world.

The sum, though, is this:

Carbon Dioxide, as confirmed once more by our United States Government, is a valuable raw material resource.

We can reclaim Carbon Dioxide from whatever source most convenient and economical to us and, then, in a process which is so efficient it can be driven by photoelectric energy, we can convert that Carbon Dioxide into the versatile fuel alcohol Methanol, which can itself then be directly and efficiently converted into Gasoline.

That sounds like "Good News" to us.

We wonder why so few other people in US Coal Country, whose livelihoods might be threatened by exploitations like Cap and Trade taxation, and whose standards of living are reduced by OPEC extortion, don't seem to see it the same way.


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