United States Patent: 9099752

Carbon Dioxide, the purported greenhouse gas that the suspect enemies of our use of Coal in the generation of abundant and affordable electric power use as one of their primary weapons in their "War On Coal", can be seen and treated as a valuable, maybe even a precious, raw material resource.

And, if we, in the United States of America, especially those of us United States citizens resident in United States Coal Country, aren't smart enough to realize that fact and/or industrious enough to do something constructive about it, our international competitors, some of whom have gotten used to living large on our collective complacency, do realize it and are doing some things about it. 

 

As can be learned via our most recent report, being made accessible by the West Virginia Coal Association via the link:

King's Fahd and Abdulaziz Convert CO2 into Alcohol and Methane | Research & Development | News; and which report concerns the recent allowance by our United States Government of:

"United States Patent 9,109,293 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide; Date: August 18, 2015; Inventors: Saleem Ur Rahman, et. al., Saudi Arabia and India; Assignees: King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia, and King Abdulaziz City for Science and Technology, Riyadh, Saudi Arabia; Abstract: An electrocatalyst for the electrochemical conversion of carbon dioxide to hydrocarbons is provided. The electrocatalyst for the electrochemical conversion of carbon dioxide includes copper material supported on carbon nanotubes. The copper material may be pure copper, copper and ruthenium, copper and iron, or copper and palladium supported on the carbon nanotubes.  ... The present invention relates to electrochemical catalysts, and particularly to an electro catalyst for the electrochemical conversion of carbon dioxide to hydrocarbons, such as methanol and methane";

Saudi Arabia, that is, OPEC, has developed technology, again as officially confirmed by our own United States Government, that enables the productive consumption of, as harvested from whatever source, Carbon Dioxide in the industrial synthesis of fuel alcohol Methanol and substitute natural gas Methane.

Methanol, as documented in that report, and as will be documented here again, can be directly and efficiently converted into Gasoline. And, it has other quite valuable applications, as well, such as serving as a substitute for petroleum-based raw materials in the manufacture of some types of high-performance and high-volume plastics and polymers.

Substitute natural gas Methane is important, as well, especially since, as can be learned for just one example in:

http://oilandgas-investments.com/2013/natural-gas/shale-gas-boom-energy-lie/; "(the available real evidence, in the view of at least one certifiable expert) all points to a simple, but game-changing conclusion: despite the shale hype, America might actually be running out of gas".

And, that, while the shale gas industry, on the sly, as can be learned for one example in:

Group launches 'Coal is Filthy' ads against TXU - Houston Chronicle; "Group launches 'Coal is Filthy' ads against TXU; Campaign partly funded by large gas company targets proposal for 11 new (coal-fired power) plants";

does its best to reduce the size of America's Coal-fired power generation fleet and increase the number of power plants fueled by gas.

In any case, we learn herein that Saudi Arabia, via the King Fahd University of Petroleum and Minerals,  coincident with the development of the Carbon Dioxide utilization technology disclosed in the above-cited "United States Patent 9,109,293 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide", wherein Carbon Dioxide is used and consumed in the synthesis of Methanol and Methane, in partnership with the King Abdulaziz City for Science and Technology, also, on their own, developed slightly different catalytic technology wherein Carbon Dioxide can be used as the key raw material in the synthesis of, again, Methanol, but, in this case, with Carbon Monoxide as the primary co-product.

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

"United States Patent 9,099,752 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide

Electrocatalyst for electrochemical conversion of carbon dioxide - KING FAHD UNIVERSITY OF PETROLEUM AND MINERALS

August 4, 2015

Inventors: Saleem Ur Rahman, et. al., Saudi Arabia and India

Assignee: King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia

Abstract: The electrocatalyst for the electrochemical conversion of carbon dioxide includes a copper material supported on titania nanotubes. The copper material may be pure copper, copper and ruthenium, or copper and iron supported on the titania nanotubes. The electrocatalyst is prepared by first dissolving copper nitrate trihydrate in deionized water to form a salt solution. Titania nanotubes are then added to the salt solution to form a suspension, which is then heated. A urea solution is added to the suspension to form the electrocatalyst in solution. The electrocatalyst is then removed from the solution. In addition to dissolving the copper nitrate trihydrate in the volume of deionized water, either iron nitrate monohydrate or ruthenium chloride may also be dissolved in the deionized water to form the salt solution.

(Note that one of the primary differences between this technology and that disclosed in the closely similar "United States Patent 9,109,293 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide" is the specification of "titania nanotubes" as opposed to "carbon nanotubes" as the support structure for the catalyst itself, which in both cases "includes a copper material", as described. The specification herein of "titania nanotubes" relates, though, to an example of very similar art actually specifically cited by King Fahd University as precedent technology upon which their innovation herein was in part founded, and about which we previously reported in:

Penn State Seeks CO2 Recycling Patent | Research & Development | News; concerning: "US Patent Application 20100213046 - Nanotube ... Photocatalytic Conversion of Carbon Dioxide; 2010; Inventors: Craig Grimes, et. al., PA; Assignee: The Penn State Research Foundation; Abstract: Nitrogen-doped titania nanotubes exhibiting catalytic activity on exposure to any one or more of ultraviolet, visible, and/or infrared radiation, or combinations thereof are disclosed. The nanotube arrays may be co-doped with one or more nonmetals and may further include co-catalyst nanoparticles. Also, methods are disclosed for use of nitrogen-doped titania nanotubes in catalytic conversion of carbon dioxide alone or in admixture with hydrogen-containing gases such as water vapor and/or other reactants as may be present or desirable into products such as hydrocarbons and hydrocarbon-containing products, hydrogen and hydrogen-containing products, carbon monoxide and other carbon-containing products, or combinations thereof".)

Claims:  A method of making an electrocatalyst for electrochemical conversion of carbon dioxide, comprising the steps of: dissolving copper nitrate trihydrate in deionized water to form a salt solution; adding titania nanotubes to the salt solution to form a suspension; heating the suspension; adding a urea solution to the suspension to form an electrocatalyst in solution, the electrocatalyst being copper material supported on the titania nanotubes; and removing the electrocatalyst from the solution, wherein the step of removing the electrocatalyst from the solution comprises the steps of: cooling the solution to room temperature; centrifuging the solution to separate the electrocatalyst out of the solution; washing and drying the electrocatalyst at a temperature of approximately 110 C; and calcining the washed and dried electrocatalyst at a temperature of approximately 450 C for approximately four hours in an argon gas flow (and, the) method of making an electrocatalyst as ... further comprising (additional steps as specified and described).

Background and Summary: The present invention relates to electrochemical catalysts, and particularly to AN electrocatalyst for the electrochemical conversion of carbon dioxide to hydrocarbons. 

Over the past several decades, various electrode materials have been researched for the reduction of carbon dioxide (CO2) into different products, most notably formic acid, carbon monoxide (CO), methane and methanol.

Conventional metals used in the research were provided in the form of high purity foils, plates, rotating discs, wires, beds of particles, tubes and mesh. These are all macroscopic materials, thus, when compared to microscopic or nanoscopic materials, they all have relatively low surface areas and low conductivity electrical supports. 

It would be desirable to provide an electrocatalytic material formed on nanostructures, thus greatly increasing available reactive surface area and conductivity. Given the destructive nature of carbon dioxide as a greenhouse gas, increasing efficiency of electrocatalysts to form benign hydrocarbons, such as methanol, is obviously quite important. Further, it would be desirable to not only increase the overall efficiency of the catalytic process, but also provide an electrocatalyst that operates under relatively low temperatures and in the range of atmospheric pressure. 

The electrocatalyst for the electrochemical conversion of carbon dioxide includes a copper material supported on titania nanotubes.

(In one experimental example), using pure copper forming 20 weight percent of the electrocatalyst, using the experimental reactor described (in previous passages not reproduced here): Maximum faradaic efficiency (9.6%) for methanol was achieved at -1.5 V. Carbon monoxide was also produced as a side product".

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Other variations of processing conditions, etc., synthesized different products from the Carbon Dioxide and the water solution of various versions of the catalytic materials. Some variations produced little of interest, and, in point of fact, the above "9.6%" efficiency "for methanol" might not sound all that exciting, except for the fact that the needed, optimum current of "1.5 V" is something that can be easily achieved by various sources of low-grade, unreliable, intermittent and non-commercial environmental sources of electricity, such as solar cells or wind mills.

So, this might be an area of enterprise where so-called "green" energy could be coupled with our economically essential Coal-fired power generation industries to maximize the products generated by, and the total value of, those Coal-fired power generation industries. 

In any case, the primary product generated from Carbon Dioxide by the process of Saudi Arabia's "United States Patent 9,099,752 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide" is Methanol, and, as seen for only one example 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; Assignee: Mitsubishi Heavy Industries, Ltd., Tokyo; Abstract: 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";

Methanol, as made from Carbon Dioxide, can be directly converted into Gasoline, in a chemical reaction that also generates enough heat energy to enable the co-production of a certain amount of electric power along with the Gasoline.

Even further, the secondary product Carbon Monoxide, generated along with Methanol from Carbon Dioxide via this Saudi Arabian technology, can, as seen for one example in our report of:

Standard Oil Carbon Monoxide + Water = Gasoline | Research & Development | News; concerning: "United States Patent 4,559,363 - Process for Reacting Carbon Monoxide and Water; 1985; Inventors: Jeffrey Miller and Albert Hensley; (Assignee: Standard Oil Company of Indiana); Abstract: A process for reacting carbon monoxide and water in the presence of a cadmium-containing catalyst is disclosed. ... This invention relates generally to the reaction between carbon monoxide and water, and more particularly concerns such reaction in the presence of a cadmium-containing catalyst. It is a general object of the present invention to provide a method for the direct production of gasoline";

also be used and consumed in the direct synthesis of Gasoline, with no other raw material needed but plain old Water.

Note, that, in our original report of "United States Patent 4,559,363", as linked above, the official United States Patent and Trademark Office electronic record of that invention, linked to in the report, is somehow corrupted, and doesn't actually name "Standard Oil" as the developer and owner of that  technology, wherein Carbon Monoxide and Water are converted into Gasoline. 

The following records:

Process for reacting carbon monoxide and water - Standard Oil Company (Indiana); and:

http://www.freepatentsonline.com/4559363.pdf;

make clear that Standard Oil Company of Indiana did, indeed, develop an efficient process wherein Carbon Monoxide, co-produced along with Methanol via the process of our subject herein, "United States Patent 9,099,752 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide", from CO2, can be directly used and consumed, with Water being the only other raw material needed, in the synthesis of, what could be and should be non-OPEC and all-American, Gasoline.


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