United States Patent Application: 0150096897

The door is open to us, if we ever find the courage within ourselves to look through it, to openly talk and communicate about what we see; and, then, to actually have the moral currents of enterprise and patriotism running though us strong enough to motivate us to actually do something with the knowledge gained.

We have the opportunity to do some great things for our nation, and, in particular, for United States Coal Country. We could start putting the economic boot to OPEC, and bring our sons and daughters in uniform home from that dangerous and unpleasant part of the world where so much oil is produced and shipped, all while we assuaged some of the worries of the environmentally-concerned among our fellow citizens - - some of them no doubt the parents of young patriots serving in the Persian Gulf area - - and, created new industries and a wealth of new jobs in United States Coal Country.

Carbon Dioxide, as we might harvest from the exhaust gases co-produced by our economically essential use of Coal in the generation of abundant and affordable electric power, is, now without doubt, a valuable raw material resource.

Carbon Dioxide can be used and consumed as the basic raw material in processes which result in the efficient production of a full range of hydrocarbon fuels and chemicals, including fuel alcohol Methanol.

One of the very major corporations with a global presence who have been demonstrating the fact that Carbon Dioxide is a valuable raw material is Japan's admirable Panasonic Corporation.

As we have seen by now in many reports, such as, for just one example:

Panasonic Solar Energy Converts More CO2 into Methane | Research & Development | News; concerning: "United States Patent 8,617,375 - Method for Reducing Carbon Dioxide; 2013; Inventors: Yugi Zenitani, Masahiro Deguchi, Satoshi Yotsuhashi, Reiko Taniguchi, Japan; Assignee: Panasonic Corporation, Osaka; Abstract: The method for reducing carbon dioxide of the present invention includes a step (a) and a step (b) as follows. A step (a) of preparing an electrochemical cell. The electrochemical cell comprises a working electrode, a counter electrode and a vessel. The vessel stores an electrolytic solution. The working electrode contains boron carbide. The electrolytic solution contains carbon dioxide. The working electrode and the counter electrode are in contact with the electrolytic solution. A step (b) of applying a negative voltage and a positive voltage to the working electrode and the counter electrode, respectively, to reduce the carbon dioxide. ... A carbon dioxide (CO2) reduction technique using a catalyst is expected as a technique for fixing CO2 and producing useful substances. ... (It) is an object of the present invention to provide a method for reducing carbon dioxide using a highly-durable catalyst that is capable of reducing CO2 at an overvoltage equal to or lower than overvoltages required for conventional catalysts to produce highly useful substances (such as formic acid (HCOOH), methane (CH4), ethylene (C2H4), and ethane (C2H6)). (Boron Carbide) used as a catalyst in reducing CO2 causes the reducing reaction of CO2 only with an external energy from DC power supply at ordinary temperature. Moreover, the method for reducing CO2 of the present invention can be applied to methods using a solar cell as an external power supply. The catalyst for reducing CO2 can be applied, by combination with a photocatalyst, to catalysts that can be used with solar energy. ... The method for reducing CO2 of the present invention can be applied to methods using a solar cell as an external power supply. The catalyst for reducing CO2 can be applied, by combination with a photocatalyst, to catalysts which can be used with solar energy. 

Industrial Applicability: The present invention demonstrates that boron carbide (B4C), which is a highly durable compound, is capable of reducing CO2 electrolytically at an overvoltage lower than overvoltage required for conventional catalysts for reducing CO2. Boron carbide makes it possible to produce CH4 (Methane) ..., etc. from CO2 with less energy. That is, the method for reducing CO2 of the present invention can provide these useful substances from CO2 at lower cost";

Panasonic has developed processes wherein Carbon Dioxide can be used and consumed in the synthesis of, perhaps most especially, substitute natural shale gas Methane.

Another valuable product which can be synthesized from Carbon Dioxide, as we've seen now in many reports, such as, for one early example:

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 (USDOE Brookhaven, NY, National Laboratory); 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. Summary: In accordance with a preferred embodiment of this invention, a solution of KOH is employed to absorb CO2 from air forming an aqueous solution of K2CO3, the solution is then electrolyzed to produce CH3OH (i.e., Methanol) and reform KOH in solution, the CH3OH is then removed, and make-up water is then added prior to repeating the aforementioned steps. Other products ... are also formed which can be separated and recovered as valuable products. By the process described above, it is seen that any source of electrical power may be employed, such as coal-fired power plants. However, from an environmental point of view ... solar energy generated power, would be preferred";

is fuel alcohol Methanol, an immensely valuable material which can, once synthesized from Carbon Dioxide, then itself be used as the key raw material in the synthesis.of even more valuable products, such as, as explained by another major Japanese company in our report of:

Japan CO2 to Methanol to Gasoline | Research & Development | News; concerning, in part: "United States Patent Application 0130014430 - Method for Generating Electricity and for Producing Gasoline from Methanol and System Therefore; 2013; Inventor: Masaki Iijima, Japan; Assignee: Mitsubishi Heavy Industries, Ltd., Tokyo; A method for generating electric power and for producing gasoline from methanol, includes the steps of: synthesizing gasoline by reacting methanol under a catalyst; recovering heat generated from the gasoline synthetic reaction of methanol by cooling the reaction with coolant to vaporize the coolant; and generating electric power by using the coolant vapor produced in the heat recovery. The power generation step may include generating electric power with a plurality of steam turbines in series, e.g., a high-pressure turbine, a medium-pressure turbine, and a low-pressure turbine. Claims: A method for generating electric power and for producing gasoline from methanol";

Gasoline, wherein the Methanol-to-Gasoline process can be designed and structured so that a certain amount of electric power can be co-produced, with the Gasoline, from such CO2-derived Methanol.

And, we learn herein that Panasonic, who have developed such efficient electrochemical processes for generating light hydrocarbons, such as "methane (CH4), ethylene (C2H4), and ethane (C2H6)", from Carbon Dioxide, as in our above-cited report concerning "United States Patent 8,617,375 - Method for Reducing Carbon Dioxide", have themselves very recently further developed more advanced technology for consuming Carbon Dioxide in the electrochemical synthesis, not of Methane, but, of Methanol - - which they accomplish through the use of different, specific materials for the catalytic electrodes in a process and device that sounds very similar in concept to that disclosed by Panasonic in "United States Patent 8,617,375", and others related to it.

As seen in excerpts from the initial and one following link in this dispatch to:

"United States Patent Application 20150096897 - Methanol Generation Device, Method for Generating Methanol, and Electrode for Generating Methanol

METHANOL GENERATION DEVICE, METHOD FOR GENERATING METHANOL, AND ELECTRODE FOR GENERATING METHANOL - Hashiba, Hiroshi

April 9, 2015

Inventors: Hiroshi Hashiba, et. al., Japan

Assignee: Panasonic Intellectual Property Management, Ltd., Osaka

Abstract: The present invention provides a methanol generation device for generating methanol by reducing carbon dioxide, comprising: a container for storing an electrolyte solution containing carbon dioxide; a cathode electrode disposed in the container so as to be in contact with the electrolyte solution; an anode electrode disposed in the container so as to be in contact with the electrolyte solution; and an external power supply for applying a voltage so that a potential of the cathode electrode is negative with respect to a potential of the anode electrode. The cathode electrode has a region of (Copper-Nickel-Gold). The anode electrode has a region of a metal or a metal compound. 

(As the full Disclosure makes clear, it is the specific elements of which the electrodes are made that make the process selective towards the production of Methanol.)

Claims: A methanol generation device for generating methanol by reducing carbon dioxide, comprising: a container for storing an electrolyte solution containing carbon dioxide; a cathode electrode disposed in the container so as to be in contact with the electrolyte solution; an anode electrode disposed in the container so as to be in contact with the electrolyte solution; and an external power supply for applying a voltage so that a potential of the cathode electrode is negative with respect to a potential of the anode electrode, wherein the cathode electrode includes a region of (Copper, Nickel and Gold in specified proportions); and the anode electrode includes a region of a metal or a metal compound. 

The methanol generation device ...  wherein the (Copper, Nickel, Gold) is a solid solution or intermetallic compound of Cu, Ni, and Au (and) wherein the anode electrode is formed of carbon, platinum, gold, silver, copper, titanium, iridium oxide, or an alloy thereof.

(Note, that, although some of the required elements are expensive, they aren't, since they serve as catalysts, consumed or "used up" to any appreciable extent in the process. They are more of a capital expense than an operating cost.) 

The methanol generation device ... wherein the electrolyte solution is a potassium chloride aqueous solution or a sodium chloride aqueous solution.

(Salt water, in other words.)

The methanol generation device ... wherein an absolute value of the voltage is not less than 2.5 volts (and) wherein the reference electrode has a region of (Silver/Silver Chloride); and the voltage to be applied by the external power supply to the cathode electrode with respect to a potential of the reference electrode is not more than -1.7 volts.

(We don't, it seems, need a lot of power to run this thing. Low-grade and intermittent wind or solar electricity, though unreliable, could well do the trick.) 

The methanol generation device ...  further comprising: a solid electrolyte membrane for dividing the container into a cathode container for storing a first electrolyte solution containing carbon dioxide and an anode container for storing a second electrolyte solution ...  wherein the first electrolyte solution is a potassium chloride aqueous solution or a sodium chloride aqueous solution; and the second electrolyte solution is a potassium hydrogen carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, or a potassium sulfate aqueous solution.

("sodium hydrogen carbonate aqueous solution" is what we've all taken for heartburn. Other labels for it are "Sodium Bicarbonate" and "Baking Soda". Think we could scramble some up?)

A method for generating methanol using a methanol generation device, the method comprising: (a) preparing the methanol generation device comprising: a container; a cathode electrode; and an anode electrode, wherein the cathode electrode includes a region of CuNiAu; the anode electrode includes a region of a metal or a metal compound; an electrolyte solution is stored in the container; the cathode electrode is in contact with the electrolyte solution; the anode electrode is in contact with the electrolyte solution; and the electrolyte solution contains carbon dioxide; and (b) reducing the carbon dioxide contained in the electrolyte solution by applying a voltage so that a potential of the cathode electrode is negative with respect to a potential of the anode electrode to generate methanol on the cathode electrode. 

The method ... wherein the methanol generation device is placed under room temperature and atmospheric pressure ... .

An electrode for generating methanol used for a methanol generation device for generating methanol by reducing carbon dioxide ... .

Background and Field: The present disclosure relates to a methanol generation device, a method for generating methanol, and an electrode for generating methanol. 

U.S. Pat. No. 5,234,768 discloses a method for reducing carbon dioxide electrochemically using a phthalocyanine metal complex.

("United States Patent: 5234768 - Gas Permeable Member; 1993; Inventor: N. Furuya, Japan; Abstract: Disclosed herein is a gas permeable member, in particular a gas permeable electrode, carrying a metal complex on a reaction layer thereof. A central metal of the complex may be selected from lead, chromium, iron, cobalt, nickel, copper, zinc, platinum, palladium, manganese, tin, vanadium or the like. The selectivity of a reaction employing the gas permeable member depends on the central metal so that the gas permeable member can be employed in a wide range of applications including electrolytic reduction of carbon dioxide by suitably selecting the central metal of the complex. The complex, for instance a Pc-complex, may be deposited from sulfuric acid by diluting the sulfuric acid by water to be uniformly dispersed in the reaction layer.)  

Summary: The present invention provides a methanol generation device for generating methanol by reducing carbon dioxide, comprising:

- a container for storing an electrolyte solution containing carbon dioxide;

- a cathode electrode disposed in the container so as to be in contact with the electrolyte solution;

- an anode electrode disposed in the container so as to be in contact with the electrolyte solution; and:

- an external power supply for applying a voltage so that a potential of the cathode electrode is negative with respect to a potential of the anode electrode (as described).

The present invention provides a methanol generation device having high methanol generation efficiency".

---------------------------- 

According to Panasonic, we can make fuel alcohol Methanol, with "high ... efficiency", in a relatively low energy, i.e., "room temperature and atmospheric pressure", process,from, as harvested from whatever convenient source, Carbon Dioxide.

And, Panasonic followed up with an immediate encore to the above "United States Patent Application 20150096897 - Methanol Generation Device, Method for Generating Methanol, and Electrode for Generating Methanol", with the identically-titled, identically-dated and sequentially-published:

United States Patent Application: 0150096898 - Methanol Generation Device, Method for Generating Methanol, and Electrode for Generating Methanol

METHANOL GENERATION DEVICE, METHOD FOR GENERATING METHANOL, AND ELECTRODE FOR GENERATING METHANOL - Hashiba, Hiroshi

April 9, 2015

Inventors: Hiroshi Hashiba, et. al., Japan

Assignee: Panasonic Intellectual Property Management, Ltd., Osaka

Abstract: The present invention provides a methanol generation device for generating methanol by reducing carbon dioxide, comprising: a container for storing an electrolyte solution containing carbon dioxide; a cathode electrode disposed in the container so as to be in contact with the electrolyte solution; an anode electrode disposed in the container so as to be in contact with the electrolyte solution; and an external power supply for applying a voltage so that a potential of the cathode electrode is negative with respect to a potential of the anode electrode. The cathode electrode includes a region of (Copper and Gold). The anode electrode includes a region of a metal or a metal compound.

Claims: A methanol generation device for generating methanol by reducing carbon dioxide, comprising: a container for storing an electrolyte solution containing carbon dioxide; a cathode electrode disposed in the container so as to be in contact with the electrolyte solution; an anode electrode disposed in the container so as to be in contact with the electrolyte solution; and an external power supply for applying a voltage so that a potential of the cathode electrode is negative with respect to a potential of the anode electrode, wherein the cathode electrode includes a region of (Copper, Cu, and Gold, Au, present in a specified range of relative amounts); and the anode electrode includes a region of a metal or a metal compound. 

The methanol generation device ... wherein the (Copper and Gold) is a solid solution or intermetallic compound of Cu and Au.

The methanol generation device ...  wherein the anode electrode is formed of carbon, platinum, gold, silver, copper, titanium, iridium oxide, or an alloy thereof.

(Again, some pricey stuff, some expensive materials, in these things; but, those materials are not actually consumed in the process. It's like buying someone a gold ring - they'll likely have it for a while.)

The methanol generation device ... wherein the electrolyte solution is a potassium chloride aqueous solution or a sodium chloride aqueous solution (and) wherein an absolute value of the voltage is not less than 2.5 volts (and) further comprising: a reference electrode disposed in the container so as to be in contact with the electrolyte solution, wherein the reference electrode has a region of Ag/AgCl; and the voltage to be applied by the external power supply to the cathode electrode with respect to a potential of the reference electrode is not more than -1.7 volt. 

The methanol generation device ...  further comprising: a solid electrolyte membrane for dividing the container into a cathode container for storing a first electrolyte solution containing carbon dioxide and an anode container for storing a second electrolyte solution (and) wherein the first electrolyte solution is a potassium chloride aqueous solution or a sodium chloride aqueous solution, and the second electrolyte solution is a potassium hydrogen carbonate aqueous solution, a sodium hydrogen carbonate aqueous solution, or a potassium sulfate aqueous solution.

A method for generating methanol using a methanol generation device, the method comprising: (a) preparing the methanol generation device comprising: a container; a cathode electrode; and an anode electrode, wherein the cathode electrode has a region of Cu-Au; the anode electrode has a region of a metal or a metal compound; an electrolyte solution is stored in the container; the cathode electrode is in contact with the electrolyte solution; the anode electrode is in contact with the electrolyte solution; and the electrolyte solution contains carbon dioxide; and (b) reducing the carbon dioxide contained in the electrolyte solution by applying a voltage so that a potential of the cathode electrode is negative with respect to a potential of the anode electrode to generate methanol on the cathode electrode.

The method ... wherein the methanol generation device is placed under room temperature and atmospheric pressure ... .

An electrode for generating methanol used for a methanol generation device for generating methanol by reducing carbon dioxide.

Background and Field: The present disclosure relates to a methanol generation device, a method for generating methanol, and an electrode for generating methanol.

Summary: The present invention provides a methanol generation device for generating methanol by reducing carbon dioxide (with) high methanol generation efficiency".

---------------------------- 

We/ll note that the Panasonic electrolytic CO2 utilization processes of our subjects, "United States Patent Application 20150096897 - Methanol Generation Device, Method for Generating Methanol, and Electrode for Generating Methanol" and "United States Patent Application 0150096898 - Methanol Generation Device, Method for Generating Methanol, and Electrode for Generating Methanol", seem closely similar in concept and in some specifics to a few more recent CO2 conversion technologies developed by respected and impeccable entities in the United States of America, as for one example seen in: 

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. 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 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 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". 

But, it is Methanol, primarily, which is efficiently synthesized from Carbon Dioxide in these Panasonic innovations. And we remind you that Methanol is an industrial feedstock of potentially immense value. Not only can Methanol be converted directly into Gasoline - - as in our above-cited report concerning "United States Patent Application 0130014430 - Method for Generating Electricity and for Producing Gasoline from Methanol and System Therefore" - - it can, as seen for just one example in our report of: 

Coal and CO2 to Gasoline and Plastics via Methanol | Research & Development | News; which contained links to separate references relating, that, in addition to the fact that Methanol can be converted directly and efficiently into Gasoline: "Methanol is already used today on a large scale ... as a raw material to produce numerous chemical products and materials. In addition, it can be readily converted in the methanol to olefin (MTO) process into ethylene and propylene, which can be used to produce synthetic hydrocarbons and their products ... . (And, Methanol can) be made from chemical recycling of carbon dioxide. Initially the major source will be the CO2 rich flue gases of fossil fuel burning power plants".

be used as a replacement for perhaps all or nearly all of the industrial organic chemical feed stocks conventionally derived from imported OPEC petroleum.

The door is open. Do we have the guts to walk through it?


West Virginia Coal Association - PO Box 3923 - Charleston, WV 25339 | 304-342-4153 | website developed by brickswithoutstraw