United States Patent: 9090976

Carbon Dioxide, contrary to all we've been led to believe, can be seen and treated as a valuable raw material resource, a raw material which can be used and consumed, instead of imported OPEC petroleum-based raw materials, in the industrial synthesis of various hydrocarbon fuels and certain high-volume plastics and polymers.

Wouldn't it be an immense blessing in terms of the United States Coal Country economy, that is, in terms of jobs and industries, if that fact were at last openly and publicly acknowledged, and, acted upon?

For instance, we've many times documented the Carbon Dioxide utilization achievements of the company, Liquid Light Chemicals, "LLC", of New Jersey, as in, for just one example, our report of:

More New Jersey CO2 to High-Energy Alcohol | Research & Development | News; concerning: "United States Patent 8,961,774 - Electrochemical Production of Butanol from Carbon Dioxide and Water; 2015; Inventors: Emily Barton Cole, Kyle Teamey, Andrew Bocarsly, and Narayanappa Sivasankar; Assignee: Liquid Light, Inc., Monmouth, NJ; Abstract: Methods and systems for electrochemical production of butanol are disclosed. A method may include, but is not limited to, steps (A) to (D). Step (A) may introduce water to a first compartment of an electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a solution of an electrolyte, a catalyst, and a cathode. Step (C) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to a product mixture. Step (D) may separate butanol from the product mixture".

In that report, it was again noted and documented that LLC actually arose to further develop and to commercialize the Carbon Dioxide utilization technologies first established in the Princeton University labs of Professor Andrew Bocarsly, like that disclosed in our report of:

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, 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, 2-propanol, acetone, acetaldehyde and mixtures thereof".

Note, in the disclosure of the above "United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products"; that, first, fuel alcohol Ethanol is one of the products that can be made via such productive recycling of, as harvested from whatever convenient source, Carbon Dioxide; and, second, that the development of that CO2 utilization technology by Princeton University was paid for, at least in part, by the National Science Foundation:

Overview - NSF at a Glance | NSF - National Science Foundation; "The National Science Foundation (NSF) is an independent federal agency created by Congress in 1950 "to promote the progress of science; to advance the national health, prosperity, and welfare; to secure the national defense…" With an annual budget of $7.3 billion (FY 2015), we are the funding source for approximately 24 percent of all federally supported basic research conducted by America’s colleges and universities. In many fields such as mathematics, computer science and the social sciences, NSF is the major source of federal backing.We fulfill our mission chiefly by issuing limited-term grants -- currently about 11,000 new awards per year, with an average duration of three years -- to fund specific research proposals that have been judged the most promising by a rigorous and objective merit-review system. Most of these awards go to individuals or small groups of investigators. Others provide funding for research centers, instruments and facilities that allow scientists, engineers and students to work at the outermost frontiers of knowledge. NSF's goals - discovery, learning, research infrastructure and stewardship - provide an integrated strategy to advance the frontiers of knowledge, cultivate a world-class, broadly inclusive science and engineering workforce and expand the scientific literacy of all citizens, build the nation's research capability through investments in advanced instrumentation and facilities, and support excellence in science and engineering research and education through a capable and responsive organization. We like to say that NSF is "where discoveries begin". Many of the discoveries and technological advances have been truly revolutionary. In the past few decades, NSF-funded researchers have won some 214 Nobel Prizes".

And, the value of NSF Grant No. CHE-0616475, as in the above "United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products", wherein technology was developed by Princeton University that enables the conversion of Carbon Dioxide into fuel alcohol Ethanol, was actually multiplied, since, as seen in our report of:

Princeton Photosynthesizes Methanol from Power Plant CO2 | Research & Development | News; concerning: "United States Patent 8,986,533 - Conversion of Carbon Dioxide to Organic Products; 2015; Inventors: Andrew Bocarsly and Emily Barton Cole, NJ; 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 into at least one product, comprising: reducing the carbon dioxide photoelectrochemically in a divided electrochemical cell ... (and) further comprising illuminating the cathode with light energy to provide energy to the cell. The method ... further comprising receiving the carbon dioxide from an exhaust stream from a fossil fuel burning power or industrial plant, from a source accompanying natural gas or from a geothermal well. 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 formic acid, formaldehyde, and methanol";

it also paid for the development, by Princeton University, of additional processes that can be powered, basically, by sunlight, and which are capable of converting Carbon Dioxide into even more products, including another important fuel alcohol, Methanol.

And, herein we learn that the National Science Foundation has also been funding, through a separate grant, the development of even more Carbon Dioxide utilization technology by both Princeton University, with some participation it seems by their commercial spin-off, Liquid Light Chemicals, and, another respected United States institution of higher learning, The University of Richmond.

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

"United States Patent 9,090,976 - Advanced Aromatic Amine Heterocyclic Catalysts for Carbon Dioxide Reduction

Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction - The Trustees of Princeton University

Date: July 28, 2015

Inventors: Andrew Bocarsly, et. al., NJ, PA, and VA

Assignees: Princeton University, NJ, and University of Richmond, VA

(Since the University of Richmond partnered with Princeton is this development, and, since that school might not be as familiar to our readers, more about it can be learned via:

University of Richmond - Wikipedia, the free encyclopedia; "The University won its first NCAA national championship in any sport on December 19, 2008 when the Spiders football team defeated the Montana Grizzlies, 24–7, in the NCAA Division I-AA Football Championship".

More about the school and about their representative on the research team who's work led to this development, one Raymond Dominey, can be learned via:

http://www.richmond.edu/http://as.richmond.edu/

Department of Chemistry - School of Arts & Sciences - University of Richmond; and:

Raymond N. Dominey - Biographical Information  "During the Spring and Summer of 2009 I made a strategic shift to focus my research more exclusively on the “Energy Problem ” -a problem which I am absolutely convinced will be THE MOST IMPORTANT PROBLEM facing society during this century. To try to impact this problem, I have established significant research collaborations with groups a Princeton University, NASA, and CalTech".)

Abstract: Methods and systems for electrochemical reduction of carbon dioxide using advanced aromatic amine heterocyclic catalysts are disclosed. A method for electrochemical reduction of carbon dioxide may include, but is not limited to, steps (A) to (C).

Step (A) may introduce water to a first compartment of an electrochemical cell. The first compartment may include an anode.

Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a solution of an electrolyte, a catalyst, and a cathode. The catalyst may include at least two aromatic amine heterocycles that are at least one of (a) fused or (b) configured to become electronically conjugated upon one electron reduction.

Step (C) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to a product mixture.

Government Interests: This invention was made with government support under Grant CHE-0911114 awarded by the National Science Foundation. The government has certain rights in the invention..

Claims:  A method for electrochemical reduction of carbon dioxide, comprising: (A) introducing water to a first compartment of an electrochemical cell, said first compartment including an anode; (B) introducing carbon dioxide to a second compartment of said electrochemical cell, said second compartment including an electrolyte, a catalyst, and a cathode, wherein said catalyst includes at least one of 4-azabenzimidazole or 7-azaindole; (C) applying an electrical potential between said anode and said cathode in said electrochemical cell sufficient for said cathode to reduce said carbon dioxide to a product mixture. 

The method ... wherein said product mixture includes at least one of a single-carbon product or a multiple-carbon product. 

The method ... wherein said anode oxidizes the water to oxygen gas. 

(The "oxygen gas" could be an industrially-valuable by-product of this CO2 utilization process.)

The method ... wherein the electrolyte (and the) catalyst (are of compositions specified).

The method ... wherein the product mixture includes ethanol (and/or) acetic acid. 

(The Claims section, as we will see, actually identifies only some of the products which can be synthesized, using the technology disclosed herein, from Carbon Dioxide.)

Description and Background: The present application is a result of activities undertaken within the scope of a Joint Research Agreement between Liquid Light, Inc. and The Trustees of Princeton University. 

(So, Liquid Light Chemicals, as well as the University of Richmond, partnered with Princeton University in the execution of National Science Foundation Grant CHE-0911114.)

The present disclosure generally relates to the field of electrochemical reactions, and more particularly to advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction. 

A mechanism for mitigating emissions is to convert carbon dioxide into economically valuable materials such as fuels and industrial chemicals. If the carbon dioxide is converted using energy from renewable sources, both mitigation of carbon dioxide emissions and conversion of renewable energy into a chemical form that can be stored for later use will be possible. 

Summary: A method for electrochemical reduction of carbon dioxide may include, but is not limited to, steps (A) to (C). Step (A) may introduce water to a first compartment of an electrochemical cell. Said first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of said electrochemical cell. Said second compartment may include a solution of an electrolyte, a catalyst, and a cathode. Said catalyst may include at least two aromatic amine heterocycles that are at least one of (a) fused or (b) configured to become electronically conjugated upon one electron reduction. Step (C) may apply an electrical potential between said anode and said cathode in said electrochemical cell sufficient for said cathode to reduce said carbon dioxide to a product mixture. 

In accordance with some embodiments of the present disclosure, an electrochemical system is provided that generally allows electrochemical reduction of carbon dioxide utilizing advanced aromatic amine heterocyclic catalysts. The electrocatalysts disclosed herein generally may allow for the formation of carbon-carbon bonded species from carbon dioxide under appropriate electrochemical conditions (e.g., electrode material, electrode potential, cathode material, and the like). Additionally, the electrocatalysts disclosed herein generally may allow for reduction of carbon dioxide to single-carbon products (e.g., methanol, formic acid, formaldehyde, and the like). Product selectivity may be obtained by the matching of electrode material, aromatic amine catalyst, electrode potential, or other electrochemical cell condition. 

Industrial synthesis of organic products using current techniques generally requires a large amount of energy, which may come from natural gas. The combustion of natural gas contributes to the concentration of carbon dioxide in the atmosphere ... .

In some embodiments of the present disclosure, the energy used by the system may be generated from an alternative energy source ...  . In general, the embodiments for the reduction of carbon dioxide do not require oil or natural gas as feedstocks.

Advantageously, the carbon dioxide for reduction in systems of the present disclosure may be obtained from any source (e.g., an exhaust stream from fossil-fuel burning power or industrial plants, from geothermal or natural gas wells or the atmosphere itself).

Most suitably, the carbon dioxide may be obtained from concentrated point sources of generation prior to being released into the atmosphere. For example, high concentration carbon dioxide sources may frequently accompany natural gas in amounts of 5% to 50% ...  and high purity carbon dioxide may be exhausted from cement factories, from fermenters used for industrial fermentation of ethanol, and from the manufacture of fertilizers and refined oil products. Certain geothermal steams may also contain significant amounts of carbon dioxide.

(The) capture and use of existing atmospheric carbon dioxide in accordance with some embodiments of the present invention generally allow the carbon dioxide to be a renewable and unlimited source of carbon. 

In case of photoelectrochemical methods, some or all of the energy for reducing the carbon dioxide comes from light that is incident on the semiconductor surfaces. The reduction of the carbon dioxide for the photoelectrochemical methods may take place on the photovoltaic material, or via a catalyst. 

The present disclosure may include use of low-cost heterocyclic amines, such as pyridine, as catalysts for carbon dioxide reduction. The process may provide good selectivity for methanol, with a 30% to 95% faradaic yield for carbon dioxide to methanol, with the remainder evolving hydrogen. The use of alternative cathode materials, alternative aromatic amine electrocatalysts, and alternative mechanisms for improving control over the reaction may provide further benefits. 

The present disclosure may provide for the use of protonated aromatic amines such as pyridine to efficiently reduce CO2 to a variety of chemicals such as methanol. The present method may further include use of substituent groups on the heterocycle, such as methyl groups or hydroxyl groups, which may be used to change the reduction product from methanol to multi-carbon containing products such as propanol. 

(Note that the valuable alcohols "methanol" and "propanol" can, in addition to Ethanol, be selected for.)

The reduction of the carbon dioxide may be suitably achieved efficiently in a divided electrochemical or photoelectrochemical cell in which (i) a compartment contains an anode suitable to oxidize or split the water, and (ii) another compartment contains a working cathode electrode and a catalyst. The compartments may be separated by a porous glass frit, microporous separator, ion exchange membrane, or other ion conducting bridge. Both compartments generally contain an aqueous solution of an electrolyte. Carbon dioxide gas may be continuously bubbled through the cathodic electrolyte solution to saturate the solution or the solution may be pre-saturated with carbon dioxide. 

(The) product mixture may include at least one of butanol, formic acid, methanol, glycolic acid, glyoxal, acetic acid, ethanol, acetone, or isopropanol. In a particular implementation, ethanol may be produced with a yield ranging from approximately 4% to 20%. In other implementation, acetic acid may be produced with an approximately 8% yield, without significant detection of other carbon-containing products. 

(One specified and described catalyst) may provide for the production of isopropanol and/or acetone from carbon dioxide at relatively low electrode potentials.

(So, other valuable products, "butanol", "isopropanaol and/or acetone", can be made from Carbon Dioxide via the process of our subject, "United States Patent 9,090,976 - Advanced Aromatic Amine Heterocyclic Catalysts for Carbon Dioxide Reduction", in addition to Ethanol and Methanol.)  

In the reduction of carbon dioxide to products, water may be oxidized (or split) to protons and oxygen at the anode  while the carbon dioxide is reduced to the product mixture at the cathode. The electrolyte in the cell may use water as a solvent with any salts that are water soluble, including potassium chloride (KCl) ... .

Product selectivity may be obtained by the matching of electrode material, aromatic amine catalyst, electrode potential, or other electrochemical cell condition. For instance, in an electrochemical system having fixed cathodes (e.g., with stainless steel 2205 cathodes), the electrolyte (such as the catholyte) may be altered to change the product mixture.

In another instance, such as with a modular electrochemical system having swappable/interchangeable cathodes, the cathode may be altered to change the product mixture. Additionally, the electrochemical system may incorporate a photoelectrochemical cell where the cathode is a light responsive p-type semiconductor or may incorporate a hybrid photoelectrochemical system where the anode is a light responsive n-type semiconductor and the cathode is a metallic electrode or a p-type light responsive semiconductor. 

As described herein, the present disclosure may include catalysts for carbon dioxide reduction featuring two or more aromatic amine heterocyclic that are either fused or become electronically conjugated upon one electron reduction. Additionally the catalysts may provide for improved energy efficiency for carbon dioxide reduction to multi-carbon products and for improved selectivity for carbon dioxide reduction to multi-carbon products".

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We've previously documented, in developments perhaps especially by Japan's Panasonic Corporation, the use of such a "photoelectrochemical system where the anode is a light responsive n-type semiconductor and the cathode is a metallic electrode or a p-type light responsive semiconductor", for the productive solar-driven conversion of Carbon Dioxide, in combination with H2O, into various "multi-carbon products".

But, in closing, as specified herein by Princeton University and the University of Richmond, among the valuable "products" which can be made so efficiently from Carbon Dioxide are "butanol", "methanol", and "ethanol".

We've previously documented that Butanol has enough energy density and inherent lubricity to be able to serve as an almost direct replacement for Gasoline. But, as seen in our report of: 

Mobil Oil 1977 Coal-Derived Alcohols to Gasoline | Research & Development | News; concerning: "US Patent 4,025,575 - Process for Manufacturing Olefins; 1977;  Assignee: Mobil Oil Corporation, NY; Abstract: A lower alcohol and/or ether feed is selectively converted to a mixture of light olefins, including ethylene and propylene, by catalytic contact of the feed, for example methanol or dimethyl ether, ... with certain crystalline aluminosilicate zeolite catalysts exemplified by HZSM-5. Claims: (A) method for converting a feed to light olefins, said feed comprising one or more compounds selected from the group consisting of the lower monohydric alcohols ... and their simple and mixed ether derivatives. (And) wherein said feed comprises methanol or dimethyl ether (and/or) ethanol";

the alcohols Methanol and Ethanol, as can also be made via the process of our subject, "United States Patent 9,090,976 - Advanced Aromatic Amine Heterocyclic Catalysts for Carbon Dioxide Reduction", from Carbon Dioxide, can then themselves be directly and efficiently converted into a full range of light hydrocarbons which can then be used, for instance, in the blending of Gasoline or in the synthesis of certain plastics and polymers, in which the CO2 consumed in the synthesis of the Methanol and Ethanol would remain permanently, and productively and profitably, "sequestered".

And, again, our United States Government officially confirmed less than one week ago, via their issuance and allowance of "United States Patent 9,090,976 - Advanced Aromatic Amine Heterocyclic Catalysts for Carbon Dioxide Reduction", that Carbon Dioxide, as can "be obtained from any source (e.g., an exhaust stream from fossil-fuel burning power or industrial plants, from geothermal or natural gas wells or the atmosphere itself", is a valuable raw material resource, the proper use of which of could enable the founding of new industries, the creation of new jobs, and generation of wealth for those nations or those regions aware enough to understand the opportunity, honest enough to publicly acknowledge it, and industrious enough to do something about it.


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