United States Patent: 8815074

Carbon Dioxide, as it arises in only a small way - - relative to some all-natural, un-taxable and non-political 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 genuinely-abundant and truly-affordable electric power, could be made to be a valuable, even a precious, raw material resource.

We could be using Carbon Dioxide to generate new industries and to create new jobs in West Virginia, Pennsylvania, and the rest of United States Coal Country, rather than, as the US EPA and other pile-on government functionaries seem to prefer, using it to kill off the economically-vital Coal-based industries, with all of their good-paying jobs, we now already have.

We've many times documented for you that technologies have been and are being developed around the world, including in the USA, which would, if reduced to industrial practice, enable us to capture Carbon Dioxide from whatever convenient source, whether our industrial stack gases or even the atmosphere itself, and then to convert that Carbon Dioxide into a full range of hydrocarbon fuels and chemicals, into virtually anything we now sell our nation out to continue purchasing from OPEC, or risk bringing carcinogenic radioactive elements to the Earth's surface by expensively fracking the abyssal shales in order to extract their penurious, although in public accounts hugely exaggerated, contents of gas.

One forward-thinking and progressive corporation which has been assertively developing the technologies needed to utilize Carbon Dioxide as an immensely valuable raw material for productive industry is Japan's admirable Panasonic Corporation.

As we've seen, for only a few out of now many examples, in the identically-titled: 

Panasonic 2013 CO2 to Methane, Formic Acid and Carbon Monoxide | Research & Development | News; concerning: "United States Patent 8,414,758 - Method for Reducing Carbon Dioxide; April 9, 2013; Inventors: Masahiro Deguchi, Satoshi Yotsuhashi, and Yuka Yamada, Japan; Assignee: Panasonic Corporation, Osaka; Abstract: A device for reducing carbon dioxide includes a cathode chamber including a cathode electrolyte solution and a cathode electrode, an anode chamber including an anode electrolyte solution and an anode electrode, and a solid electrolyte membrane. The anode electrode includes a nitride semiconductor region on which a metal layer is formed. The metal layer includes at least one of nickel and titanium. A method for reducing carbon dioxide by using a device for reducing carbon dioxide includes steps of providing carbon dioxide into the cathode solution, and irradiating at least part of the nitride semiconductor region and the metal layer with a light having a wavelength of 250 nanometers to 400 nanometers, thereby reducing the carbon dioxide contained in the cathode electrolyte solution. ... The method ... wherein ... the device is left at a room temperature and under atmospheric pressure. (Note the above implications for efficiency and economy. Basically, the only energy that needs supplied to this device and method is light of the appropriate wavelength; i.e., sunshine.) The method ... wherein ... formic acid (and/or) carbon monoxide (and/or) methane is obtained"; and:

Panasonic Photosynthesizes More Hydrocarbons from CO2Panasonic Photosynthesizes More Hydrocarbons from CO2 | Research & Develo; concerning: "United States Patent 8,709,227 - Method for Reducing Carbon Dioxide; April 29, 2014; Inventors: Masahiro Deguchi, et. al., Japan; Assignee: Panasonic Corporation; 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";

Panasonic has developed an extraordinary, even revolutionary, body of technology that would, if we were bright enough to stop our global warming CO2 bickering, entertaining though such bickering might be, and to grasp the reins of, could enable us to, in processes driven by nothing more than simple sunlight, processes which might be thought of as "artificial photosynthesis", consume Carbon Dioxide as the basic raw material for the synthesis of hydrocarbon fuels and chemicals.

The above are only a few selections chosen from Panasonic's catalogue of Carbon Dioxide utilization technologies about which we've already reported. But, in our excerpts from their "United States Patent 8,709,227 - Method for Reducing Carbon Dioxide", note that "formic acid" is one of the products specified to be derived from Carbon Dioxide.

Formic Acid is a product of Carbon Dioxide recycling technologies developed in other nations of the world, as well, including the United States of America, as we've previously documented for you. And, as seen in our report of: 

Japan Converts CO2 to Formic Acid | Research & Development | News; "US Patent 7,479,570 - Process for the Reduction of Carbon Dioxide; 2009; Inventor: Seiji Ogo, et. al., Japan; Assignee: Japan Science and Technology Agency; Abstract: Carbon dioxide and water are mixed with an organometallic complex (of varied and specified compositions). This makes it possible to directly reduce carbon dioxide in water. Claims:  A reducing process of carbon dioxide, comprising mixing carbon dioxide and water with an organometallic complex ... so as to reduce carbon dioxide so that formic acid or alkali salt thereof is formed";

other companies in Japan, in addition to Panasonic, have developed technologies for consuming Carbon Dioxide in the synthesis of, primarily and specifically, Formic Acid.

That might not sound like a particularly exciting product to be shooting for, since, if you bother to look up what the current primary uses of Formic Acid might be, one of it's major applications seems to be as a preservative for silage. There is a growing use for it in fuel cells, but those are energy applications somewhat limited in scope, currently. And, as we've documented in a few other reports, Formic Acid can actually serve in some technologies for the hydrogenation of Coal.

Those uses, and possible uses, of Formic Acid aside, there are other and much more intriguing ways in which it can be utilized that have earlier been suggested, but which remained undeveloped.

That is changing.

Some companies are now applying themselves to developing better technologies for the consumption and the much more profitable use of Formic Acid, as that Formic Acid might be derived from Carbon Dioxide.

Formic Acid, as we will see in some reports to follow, is being treated as an energy-efficient intermediate product in the transformation of Carbon Dioxide back into hydrocarbon fuels.

To that end, forward-looking and responsible companies, such as Japan's Panasonic Corporation, are focusing attention now on developing even better technologies, like the above-cited "United States Patent 7,479,570 - Process for the Reduction of Carbon Dioxide", for the consumption of Carbon Dioxide in the production of, specifically and primarily, Formic Acid.

As seen in, and as we attempt to explain in closing comment appended to, excerpts from the initial link in this dispatch to the very recent disclosure of yet another Panasonic Corporation technology for chemically "reducing" CO2:

"United States Patent 8,815,074 - Method for Reducing Carbon Dioxide

Method for reducing carbon dioxide - Panasonic Corporation

Date: August 26, 2014

Inventors: Reiko Taniguchi and Satoshi Yatsuhashi, Japan

Assignee: Panasonic Corporation, Osaka

Abstract: A method for reducing carbon dioxide with use of a device for reducing carbon dioxide includes steps of (a) preparing the device. The device includes a vessel, a cathode electrode and an anode electrode. An electrolytic solution is stored in the vessel, the cathode electrode contains a copper rubeanate metal organic framework, the copper rubeanate metal organic framework is in contact with the electrolytic solution, the anode electrode is in contact with the electrolytic solution, and the electrolytic solution contains carbon dioxide. The method further includes step of (b) applying a voltage difference between the cathode electrode and the anode electrode so as to reduce the carbon dioxide.

(Concerning the above "copper rubeanate", as exotic, and perhaps as expensive, as it might sound, we don't have the skills or knowledge to truly understand, much less to explain, the chemical structure ourselves. However, the only elements compounded in the "rubeanate", as other references we've consulted attest, are inexpensive Copper, Sulfur, Nitrogen and Hydrogen - none of which is consumed in the reactions, in any case. The Eastman company, in the United States, began developing copper rubeanate back in the 1960's for use in photo-lithography. And, although it hasn't yet been published by the United States Patent and Trademark Office or the World Intellectual Property Organization, Panasonic has applied for a Japanese patent on a "copper rubeanate" compound specifically for use in the Carbon Dioxide reduction process of our subject, "United States Patent 8,815,074 - Method for Reducing Carbon Dioxide". Documentation of all the above can be provided if wanted or needed.)

Claims: A method for reducing carbon dioxide with use of a device for reducing carbon dioxide, the method comprising steps of:

(a) preparing the device, wherein: the device comprises: a vessel; a cathode electrode; and an anode electrode, an electrolytic solution is stored in the vessel, the cathode electrode contains a copper rubeanate metal organic framework, the copper rubeanate metal organic framework is in contact with the electrolytic solution, the anode electrode is in contact with the electrolytic solution, and the electrolytic solution contains carbon dioxide; and:

(b) applying a voltage difference between the cathode electrode and the anode electrode so as to reduce the carbon dioxide. 

The method ... wherein: the vessel comprises a solid electrolyte membrane, and the solid electrolyte membrane is interposed between the cathode electrode and the anode electrode (and) wherein in the step (b), the voltage difference is not less than 2 volts. 

The method ... wherein in the step (b), the carbon dioxide is reduced on the cathode electrode (and) wherein in the step (b), formic acid is generated on the cathode electrode. 

The method ... wherein the copper rubeanate metal organic framework has the (molecular structure described and specified in appended documentation).

A method for generating formic acid, the method comprising steps of:

(a) preparing a device, wherein: the device comprises: a vessel; a cathode electrode; and an anode electrode, an electrolytic solution is stored in the vessel, the cathode electrode contains a copper rubeanate metal organic framework, the copper rubeanate metal organic framework is in contact with the electrolytic solution, the anode electrode is in contact with the electrolytic solution, the electrolytic solution contains carbon dioxide; and:

(b) applying a voltage difference between the cathode electrode and the anode electrode so as to generate the formic acid. 

Background and Summary: According to (one) aspect of the present disclosure, a method for generating formic acid includes the following steps (a) and (b). In step (a), a device is prepared. The device includes a vessel, a cathode electrode, and an anode electrode. An electrolytic solution is stored in the vessel. The cathode electrode contains a copper rubeanate metal organic framework and the copper rubeanate metal organic framework is in contact with the electrolytic solution.

The anode electrode is in contact with the electrolytic solution, and the electrolytic solution contains carbon dioxide.

In step (b), a voltage is applied difference between the cathode electrode and the anode electrode so as to generate the formic acid. 

The copper rubeanate metal organic framework may be found in Japanese laid-open patent application publication No. Hei 05-074458.

(The above is as per our earlier inserted comments. If and when "Hei 05-074448" is published by either the USPTO or the WIPO, we might link to those publications in future reports concerning the consumption of Carbon Dioxide in the synthesis of Formic Acid, and the uses to which Formic Acid can be put.)

It is preferable that a solid electrolyte membrane .. is provided in the vessel. ... An example of the solid electrolyte membrane is a Nafion (registered trademark) film available from Du Pont Kabushiki Kaisha.

(The DuPont membrane, as explained in the full documentation, serves to help collect and isolate the Formic Acid, and to help prevent the Formic Acid from decomposing back into Carbon Dioxide in the electrolytic environment. It's a pretty thoroughly thought-out technology. And, the specified Dupont product is established and commercialized, having been first developed in the 1960's, with uses currently in fuel cells and industrial Hydrogen separation, among other things. More about it can be learned via:

Nafion - Wikipedia, the free encyclopedia; "Nafion's superior properties make it suitable for a broad range of applications. Nafion has found use in fuel cells, electrochemical devices, chlor-alkali production, metal-ion recovery, water electrolysis, plating, surface treatment of metals, batteries, sensors ... and superacid catalysis for the production of fine chemicals".

It is in commercial usage now, and, in addition to being a membrane "separator" of chemical ions, also possesses catalytic properties that help drive some reactions, including, apparently, the separation of Hydrogen from the water molecule.) 

The present disclosure provides a novel method for reducing carbon dioxide. In particular, the disclosed methods are efficient in producing formic acid.

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There are a few things which need to be explained a bit, as we indicated in our introductory comments.

The full Disclosure, with it's experimental/demonstration examples, reveals that this process was designed to specifically produce, while consuming Carbon Dioxide as the primary raw material, Formic Acid.

It clearly indicates that, with some adjustments in process, this basic technology can also consume Carbon Dioxide in the synthesis of Methane, Ethane and Ethylene.

Further: The claim/specification that "the voltage difference is not less than 2 volts" is more of a generalization than a specification. Appended experimental results show that total voltage differences between the electrodes, the cathode and the anode, of a good bit less than ten volts can achieve Carbon Dioxide conversion/consumption rates of right around 90% and Formic Acid selectivity in the product mix also right around 90%.

For an industrial process, that's pretty good.

And, the potential clearly exists to use low-grade and intermittent forms of environmentally-derived electricity, such as from wind or solar, which would, because of their low-level power and intermittency, be unsuitable for addition to the grid, as the source of energy to drive the conversion of Carbon Dioxide and Water - Oxygen is a byproduct of this technology, by the way - into, primarily, Formic Acid.

As we indicated in our opening comments, there are now being disclosed, as we will be documenting in a future report or two, some good reasons why we might want to select for Formic Acid, as herein, as opposed to the other potential products, such as Methane or Ethylene, as the primary compound to make from Carbon Dioxide - a naturally-occurring chemical so non-toxic we inhale and exhale it with every breath, and which we can now start to think of and treat as a raw material of almost immense intrinsic value.


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