United States Patent: 8663447

Looking back, we've made quite a few reports to you by now documenting the plain fact that Princeton University, primarily through the team of Professor Andrew Bocarsly and his former student, now-Doctor Emily Barton Cole, has established the technology by which Carbon Dioxide, as recovered from whatever handy source, can be directly and efficiently converted into a number of valuable products, including several different fuel alcohols. 

So notable are their achievements in the field of Carbon Dioxide utilization that, as seen for example 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; 2012; Inventors: Andrew Bocarsly and Emily Barton Cole, NJ; Assignee: Princeton University; 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";

our United States Government has elected to provide at least some support for their efforts. And, as seen for one example in:

The USDOE and New Jersey Convert CO2 into Ethanol | Research & Development | News; concerning: "United States Patent Application 20130199937 - Reducing Carbon Dioxide to Products; 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 (and) wherein said products comprise one or more of acetaldehyde, acetate, acetic acid, acetone, 1-butanol, 2-butanol, 2-butanone, carbon, carbon monoxide, carbonates, ethane, ethanol, ethylene, formaldehyde, formate, formic acid, glycolate, glycolic acid, glyoxal, glyoxylate, glyoxylic acid, graphite, isopropanol, lactate, lactic acid, methane, methanol, oxalate, oxalic acid, a polymer containing carbon dioxide, 1-propanal, 1-propanol, and propionic acid";

so effective and promising are the CO2-recycling technologies developed by Bocarsly and Cole and their associates that the US Government has continued to fund the further development of those technologies at the company "Liquid Light", which is described as a "spin-off" from Princeton University which was formed to commercialize the Carbon Dioxide utilization science first established in Dr. Bocarsly's Princeton lab.

And, herein we see that one of those CO2 conversion processes developed at Princeton University, in part at least with US Government funding, was just quite recently recognized by our US Government as being both unique and practicable Carbon Dioxide utilization technology, one which is actually founded on CO2 consumption and conversion processes first developed by and for the US Government several decades ago.

As seen, with comment inserted and appended, in excerpts from the initial link in this dispatch to:

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

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

(Note, that, even though the Princeton spin-off, Liquid Light, is taking the lead in commercializing these CO2 utilization technologies, Professor Bocarsly's Princeton lab, as seen via:

http://abbgroup.mycpanel.princeton.edu/co2; wherein we're told, that: "renewable energy could be stored in the form of liquid fuels with CO2 as the feedstock. ... The Bocarsly group seeks to uncover the mechanism of CO2 electrochemical- and photoelectrochemical-reduction";

is still actively developing them.)

 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.

(At this point in the full patent document, related prior art US and foreign patents are listed. Among those in which the process of our subject, "United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products", specifically has it roots are those seen, for several examples, in our reports of:

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"; and: 

Chicago Recycles CO2 to Methanol | Research & Development | News; concerning: "United States Patent 4,609,441 - Electrochemical Reduction of Aqueous Carbon Dioxide to Methanol; 1986; Inventor: Karl Frese, et. al, California; Assignee: Gas Research Institute, Chicago; Abstract: A method of producing methanol from carbon dioxide is set forth. A solution of carbon dioxide in an aqueous solvent having electrolyte dissolved therein is electrolyzed utilizing a molybdenum cathode. Faradaic efficiency is generally quite high and without detectable corrosion.Claims: A method of producing methanol from carbon dioxide (which comprises) electrolyzing a solution of carbon dioxide in an aqueous solvent having an electrolyte therein and utilizing a cathode which comprises molybdenum to produce methanol. Field: The invention relates to the electrochemical reduction of aqueous carbon dioxide to form methanol"; and:

California Recycles More and More Carbon Dioxide | Research & Development | News; concerning, among others, two US Patents specifically cited by Princeton University herein: "United States Patent 7,704,369 - Electrolysis of Carbon Dioxide ... for Production of Methanol; 2010; Inventors: George Olah and Surya Prakash, CA; 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, industrial exhaust gases or the atmosphere itself"; and: "United States Patent 7,378,561 - Producing ... Synthetic Hydrocarbons from Carbon Dioxide and Water; 2008; Inventors: George Olah and Robert Aniszfeld, CA; Assignee: University of Southern California, Los Angeles; Abstract: A method for producing methanol and dimethyl ether using the air as the sole source of materials is disclosed. The invention relates to a method for separating the water (i.e., the moisture in the air) and carbon dioxide content of atmospheric air for their use in the subsequent production of methanol, dimethyl ether and derived synthetic hydrocarbons as products. The method includes the conversion of carbon dioxide and water under conditions sufficient to produce methanol and/or dimethyl ether. Methanol and/or dimethyl ether can be used as fuel or fuel additives or further converted to synthetic hydrocarbons and their products. Carbon dioxide is captured on a suitable absorbent, preferentially polyethyleneimine supported on nano-structured fumed silica. The process can also involve hydrogenation with hydrogen produced by electrolysis of water obtained from the air or from any other water source. Methanol can be dehydrated to produce dimethyl ether or further processed to produce synthetic hydrocarbons, polymers, and products derived from them by other known methods".)

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: 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, by the way, is the one and only claim made, and confirmed, by this US Patent. In that regard, it is remarkable, as well. Most US Patents contain multiple, sometimes a dozen or more, specific claims. This has one: "electrochemically reducing carbon dioxide ... to produce methanol".)

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. 

For production of methanol, the reduction of carbon dioxide proceeds along (the defined chemical) 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.

(The) use of electrochemical or photoelectrochemical reduction of carbon dioxide (CO2), tailored with certain electrocatalysts, produces methanol and related products in a high yield of about 60 to about 100%, based on the amount of CO2, suitably about 75 to 90%, and more suitably about 85 to 95%. At an electric potential of about -0.09 to -0.5 V with respect to a standard calomel electrode (SCE), methanol can be produced with good faradaic efficiency at the cathode"

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In other words, with electric power being supplied at one half of one volt, or even much less, which a modern photocell array of modest size ought to be able to gin itself up to providing even in the often-cloudy confines of US Coal Country, we can start converting Carbon Dioxide, as it's "bubbled through" a water solution of the specified catalysts, with "good ... efficiency", into "about 100%" Methanol.

Methanol can, by the way, be used and consumed in the synthesis of certain plastics and polymers, wherein the CO2 consumed in the synthesis of the Methanol, via the process of our subject herein, "United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products", would be forever chemically, and productively, "sequestered". Or, as seen for example 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; Claims: A process for the production of methanol from a carbonaceous feed material (by) gasifying said 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; Claims:  (A) method for converting methanol to gasoline";

Methanol, no matter which of our abundant natural resources we make it from - - whether, as above, Coal, or, as in the process of our subject herein, Princeton University's quite recently-awarded "United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products", Carbon Dioxide - - can itself then be efficiently converted into the stuff we squander our grandchildren's inheritance and endanger our entire nation's security to continue buying from the alien, and often unfriendly, powers of OPEC.  

Carbon Dioxide, as it 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 truly abundant, truly affordable and truly reliable electric power, is a valuable raw material resource.

As recently confirmed by experts in the employ of our United States Government, through their award of our subject herein, "United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products", to Princeton University, we can reclaim Carbon Dioxide from any convenient source, and, then, convert it at a "yield" perhaps as high as "100%" into the immensely versatile and valuable fuel alcohol and industrial raw material, Methanol.


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