United States Patent: 8961774

In a report now accessible on the West Virginia Coal Association's web site via the link:

New Jersey CO2 to High-Energy Alcohol | Research & Development | News;

we documented: 

"United States Patent Application 20120132538 - Electrochemical Production of Butanol from Carbon Dioxide and Water; 2012; Inventors: Emily Barton Cole, Andrew Bocarsly, et. al., NJ and DC; 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".

The product "butanol", as we've previously reported, is an alcohol with higher energy content than either the better-known Methanol or Ethanol; which high energy density, combined with other of Butanol's physical properties, allow Butanol to serve as an almost direct substitute for Gasoline.

More about that can be learned via: 

http://fortune.com/2013/04/12/the-fuel-that-could-be-the-end-of-ethanol/; "The Fuel That Could Be The End Of Ethanol".

And, herein we learn that our United States Government, a little more than a week ago, confirmed the practicability of "United States Patent Application 20120132538 - Electrochemical Production of Butanol from Carbon Dioxide and Water", via their issuance of, as excerpted from the initial link in this dispatch:

"United States Patent 8,961,774 - Electrochemical Production of Butanol from Carbon Dioxide and Water

Electrochemical production of butanol from carbon dioxide and water - Liquid Light, Inc.

February 24, 2015

Inventors: Emily Barton Cole, Kyle Teamey, Andrew Bocarsly, and Narayanappa Sivasankar

Assignee: Liquid Light, Inc., Monmouth, NJ

(We've made mention of the New Jersey CO2-recycling company, Liquid Light, many times in the course of our reportage. As can be learned separately via:  

Liquid Light | Make carbon dioxide a practical feedstock for multi-carbon chemicals; "Liquid Light develops and licenses process technology to make major chemicals from ... carbon dioxide"; and:

Princeton University - Startup born in Princeton lab turns carbon dioxide into fuels;

Liquid Light is a "spin-off", so to speak, formed to commercialize and to further develop the Carbon Dioxide utilization technologies originating, as for two examples in our reports 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"; and:

Princeton University March, 2014, CO2 to Methanol | Research & Development | News; concerning:"United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products; 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. 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";

in the Princeton University laboratories of Professor Andrew Bocarsly.)

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.

(At this point in the full Disclosure, as published by the United States Patent and Trademark Office, Liquid Light provides and extensive, exhaustive list of related US and world patent and scientific literature as evidence of prior and supportive art and technology. This invention is thoroughly grounded on established and irrefutable science. But, further, we'll note that the subject product "Butanol" is only one of the valuable compounds which can be generated via the disclosed process from Carbon Dioxide, although it is the one with the highest fuel value. As we will address to a certain extent further on, and as Liquid Light makes clear in the full Disclosure, multiple valuable alcohols and additional organic chemicals can be produced. The specific process herein is designed to maximize the recovery of Butanol.)

Claims: A method for electrochemical production of butanol, comprising:

(A) introducing water to a first compartment of a first electrochemical cell, said first compartment including an anode;

(B) introducing carbon dioxide to a second compartment of said first electrochemical cell, said second compartment including a solution of an electrolyte, a catalyst, and a cathode;

(C) applying an electrical potential between said anode and said cathode in said first electrochemical cell sufficient for said cathode to reduce said carbon dioxide to an intermediate product mixture;

(D) separating a two-carbon intermediate from said intermediate product mixture;

(E) introducing said two-carbon intermediate to a second electrochemical cell, wherein

(i) said second electrochemical cell including an anode in a first cell compartment and a cathode in a second cell compartment and:

(ii) said cathode reducing said two-carbon intermediate to a product mixture; and:

(F) separating butanol from said product mixture.

The method ... wherein said two-carbon intermediate includes at least one of glyoxal, oxalic acid, glyoxylic acid, glycolic acid, acetic acid, or acetaldehyde.

(The above could be treated as products in and of themselves.)

The method ... wherein said solution of electrolyte includes potassium chloride (and) wherein said cathode of said first electrochemical cell includes a cathode material for reducing said carbon dioxide to said intermediate product mixture, said cathode material including at least one of indium, tin, molybdenum, 316 stainless steel, nickel 625, nickel 600, nickel-chromium, elgiloy, copper-nickel, iron, iron alloy, steel, steel alloy, cobalt, cobalt alloy, chromium, or chromium alloy. 

The method (wherein) said catalyst of said first electrochemical cell includes a heterocycle catalyst (which) includes at least one of pyridine, quinoline, 1-methyl imidazole, or 4,4' bipyridine.

The method ... further comprising: adjusting a pH of the second compartment of the first cell between approximately 5 and approximately 8 (and) wherein said (product) butanol includes 2-butanol.

Background and Field: The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical production of butanol from carbon dioxide and water. 

A mechanism for mitigating emissions (of CO2) 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. 

(Existing) electrochemical and photochemical processes/systems have one or more of the following problems that prevent commercialization on a large scale. Several processes utilize metals, such as ruthenium or gold, that are rare and expensive. In other processes, organic solvents were used that made scaling the process difficult because of the costs and availability of the solvents ... . Copper, silver and gold have been found to reduce carbon dioxide to various products, however, the electrodes are quickly "poisoned" by undesirable reactions on the electrode and often cease to work in less than an hour. Similarly, gallium-based semiconductors reduce carbon dioxide, but rapidly dissolve in water.

(We've documented use of all the above metals as CO2 chemical reduction/conversion catalysts in previous reports. However, as seen for one example in: 

Panasonic Photosynthesizes More Hydrocarbons from CO2Panasonic Photosynthesizes More Hydrocarbons from CO2 | Research & Develo; concerning both:

"United States Patent 8,709,227 - Method for Reducing Carbon Dioxide; 2014; Inventors: Masahiro Deguchi, et. al., Japan;Assignee: Panasonic Corporation, Osaka; Abstract: A method for reducing carbon dioxide utilizes a carbon dioxide reduction device including a cathode chamber, an anode chamber, a solid electrolyte membrane, a cathode electrode and anode electrode. The cathode electrode includes copper or copper compound. The anode electrode includes a region formed of a nitride semiconductor layer where an Aluminum-Gallium Nitride layer and a Gallium Nitride layer are stacked. The anode electrode is irradiated with a light having a wavelength of not more than 350 nanometers to reduce the carbon dioxide on the cathode electrode. ... The method ... wherein ... the carbon dioxide reduction device is placed under a room temperature and under an atmospheric pressure (and) wherein ... at least formic acid (or) carbon monoxide (or) at least hydrocarbon is obtained"; and:

"United States Patent 8,709,228 - Method for Reducing Carbon Dioxide; 2014; Inventors: Masahiro Deguchi, et. al., Japan; Assignee: Panasonic Corporation, Osaka; Abstract: A method for reducing carbon dioxide utilizes a carbon dioxide reduction device including a cathode chamber, an anode chamber, a solid electrolyte membrane, a cathode electrode and anode electrode. The cathode electrode includes indium or indium compound. The anode electrode includes a region formed of a nitride semiconductor layer where an Aluminum-Gallium Nitride layer and a Gallium Nitride layer are stacked. The anode electrode is irradiated with a light having a wavelength of not more than 350 nanometers to reduce the carbon dioxide on the cathode electrode. The method ... wherein ... at least one of formic acid, carbon monoxide and hydrocarbon is obtained";

other companies seem to have found ways in which some of the shortcomings of the other CO2 reduction catalysts cited by Liquid Light, such as "gallium", can be overcome.)

Many cathodes produce a mixture of organic products. For instance, copper produces a mixture of gases and liquids including carbon monoxide, methane, formic acid, ethylene, and ethanol. Such mixtures of products make extraction and purification of the products costly and can result in undesirable waste products that must be disposed. Much of the work done to date on carbon dioxide reduction is inefficient because of high electrical potentials utilized, low faradaic yields of desired products, and/or high pressure operation. The energy consumed for reducing carbon dioxide thus becomes prohibitive. Many conventional carbon dioxide reduction techniques have very low rates of reaction. For example, in order to provide economic feasibility, a commercial system currently may require densities in excess of 100 milliamperes per centimeter squared (mA/cm.sup.2), while rates achieved in the laboratory are orders of magnitude less.

Summary: A method for electrochemical reduction of carbon dioxide to produce butanol 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.

Another method for electrochemical reduction of carbon dioxide to produce butanol may include, but is not limited to, steps (A) to (F). Step (A) may introduce water to a first compartment of a first electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the first 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 first electrochemical cell sufficient for the cathode to reduce the carbon dioxide to an intermediate product mixture. Step (D) may separate a two-carbon intermediate from the intermediate product mixture. Step (E) may introduce the two-carbon intermediate to a second electrochemical cell. The second electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode may reduce the two-carbon intermediate to a product mixture. Step (F) may separate butanol from the product mixture.

A system for electrochemical reduction of carbon dioxide to produce butanol may include, but is not limited to, a first electrochemical cell including a first cell compartment, an anode positioned within the first cell compartment, a second cell compartment, a separator interposed between the first cell compartment and the second cell compartment, and a cathode and a catalyst positioned within the second cell compartment. The system may also include a carbon dioxide source, where the carbon dioxide source is coupled with the second cell compartment and is configured to supply carbon dioxide to the cathode for reduction of the carbon dioxide to an intermediate product mixture. The system may also include an extractor configured to separate a two-carbon intermediate from the product mixture. The system may further include a second electrochemical cell configured to receive the two-carbon intermediate. The second electrochemical cell may include a first cell compartment, an anode positioned within the first cell compartment, a second cell compartment, a separator interposed between the first cell compartment of the second electrochemical cell and the second cell compartment of the second electrochemical cell, and a cathode positioned within the second cell compartment of the second electrochemical cell. The cathode of the second electrochemical cell may be configured to reduce the two-carbon intermediate to butanol.

In accordance with some embodiments of the present disclosure, an electrochemical system is provided that generally allows carbon dioxide and water to be converted to butanol. In some embodiments, the production of butanol from carbon dioxide and water may occur in a one-stage or a two-stage process. In the one-stage process, butanol may be produced with low yields and low selectivity. In the two-stage process, butanol may be produced with improved reaction rates, yield, and selectivity as compared to the direct conversion of carbon dioxide and water to butanol in the one-stage process.

Butanol (which includes the isomer 2-butanol, also called sec-butanol, and the isomer 1-butanol, also called n-butanol) is an industrial chemical used around the world. Industrially, butanol is produced via gas phase chemistry, using oil and natural gas as feedstocks. ... In addition to using non-renewable oil and natural gas as feedstocks, the overall process of industrially synthesizing butanol using current techniques requires a large amount of energy, which generally comes from natural gas.

Additional production techniques for butanol include production of butanol via biological pathways. However, such biological processes can be resource intensive due to the large amounts of land, fertilizer, and water necessary to grow the crops used to sustain fermentation processes.

(We have previously documented, and will likely, just to be thorough, make further report of some of the biological techniques for making Butanol out of Carbon Dioxide. In general, though, we agree with Liquid Light's assessment that such bio-based processes are hampered by a number of inefficiencies.)   

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 production of butanol from carbon dioxide and water do not require oil or natural gas as feedstocks. Some embodiments of the present invention thus relate to environmentally beneficial methods and systems for reducing carbon dioxide ... . 

A use of electrochemical or photoelectrochemical reduction of carbon dioxide and water, tailored with certain electrocatalysts, may produce butanol in a yield of approximately less than 10% as a relative percentage of carbon-containing products, particularly when metallic cathode materials are employed. 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.

(In other words, Butanol is only one of the "carbon-containing products" which can be synthesized using this method from Carbon Dioxide.)

Advantageously, the carbon dioxide 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 carbon dioxide emissions from varied industries, including geothermal wells, may be captured on-site. Separation of the carbon dioxide from such exhausts is known. Thus, 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.

The cell ... may be implemented as a divided cell. The divided cell may be a divided electrochemical cell and/or a divided photochemical cell. The cell ...  is generally operational to reduce carbon dioxide (CO2) into butanol. The reduction generally takes place by bubbling carbon dioxide and an aqueous solution of an electrolyte in the cell. A cathode in the cell may reduce the carbon dioxide into a product mixture that may include one or more compounds. For instance, the product mixture may include at least one of butanol, formic acid, methanol, glycolic acid, glyoxal, acetic acid, ethanol, acetone, or isopropanol. In particular implementations, butanol may account for less than approximately 10% of the total yield of organic compounds in the product mixture.

The liquid source may implement a water source. The liquid source may be operational to provide pure water to the cell.

In the reduction of carbon dioxide to butanol, 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) and with a suitable catalyst, such as an imidazole catalyst, a pyridine catalyst, or a substituted variant of imidazole or pyridine. Cathode materials generally include any conductor. However, efficiency of the process may be selectively increased by employing a catalyst/cathode combination selective for reduction of carbon dioxide to butanol (and/or other compounds included in the product mixture). For catalytic reduction of carbon dioxide, the cathode materials may include ... alloys of Cu and Ni. The materials may be in bulk form. Additionally and/or alternatively, the materials may be present as particles or nanoparticles loaded onto a substrate, such as graphite, carbon fiber, or other conductor.

Products other than butanol in the product mixture (e.g., formic acid, acetic acid, methanol, ethanol, acetone, and/or propanol) may be reaction intermediates. For instance, because the reaction to produce butanol requires a transfer of 24 electrons and protons, butanol production may be likely to be kinetically limited relative to reaction intermediates that require fewer electron and proton transfers. For greater selectivity, yield, and reaction rates, the two-stage process for producing butanol from carbon dioxide and water may be employed. The two-stage process includes two cells ... ".

----------------------------- 

In point of fact, as we noted in earlier comments, Butanol is only one of the products generated from Carbon Dioxide by the process of our subject, "United States Patent 8,961,774 - Electrochemical Production of Butanol from Carbon Dioxide and Water". 

But, the associated products, such as "methanol" and "ethanol",  have value, as well, and, as Liquid Light goes on to describe, some of those other products can themselves be further converted into more of the desired Butanol in a more complex "two-stage process". Otherwise, they do of course have value and use in and of themselves, and Liquid Light explains how they can be separated, if desired, from the "product mixture".

And, in sum, we have herein even further official confirmation by our United States Government, through their allowance of our subject, "United States Patent 8,961,774 - Electrochemical Production of Butanol from Carbon Dioxide and Water", that Carbon Dioxide, as we might harvest from "an exhaust stream from fossil-fuel burning power or industrial plants", can be seen and treated as a valuable raw material resource, a resource which, if the facts were made known and acted upon, could lead to the creation of new industries and new jobs in United States Coal Country, and an ultimate independence in our supply of needed hydrocarbon fuels and organic chemicals for the entire United States of America.


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