United States Patent: 9109293

We first remind you of an earlier report:

Saudi Arabia Converts Exhaust Gas CO2 into Hydrocarbons | Research & Development | News; which centered on:

"United States Patent 8,596,047 - Vehicle Electrocatalyzer for Recycling Carbon Dioxide to Fuel Hydrocarbons; 2013; Inventors: R. A. K. Shawabkeh, et. al., Saudi Arabia; Assignees: King Fahd University of Petroleum and Minerals and King Abdulaziz City for Science and Technology";

 

and which report contained additional information concerning another King Fahd and King Abdulaziz technology about which we had also earlier reported:

"United States Patent Application 20130256123 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide; October 3, 2013; Inventors: Saleem Ur Rahman, et. al., Saudi Arabia and India; Assignees: King Abdulaziz City for Science and Technology and King Fahd University of Petroleum and Minerals; 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 electrocatalyst is prepared by dissolving copper nitrate trihydrate in deionized water to form a salt solution. Carbon 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 deionized water, either iron nitrate monohydrate, ruthenium chloride or palladium chloride may also be dissolved in the deionized water to form the salt solution. Claims: An electrocatalyst for electrochemical conversion of carbon dioxide, comprising a copper catalyst material supported on carbon nanotubes. Background and Field: The present invention relates to electrochemical catalysts, and particularly to an electrocatalyst for the electrochemical conversion of carbon dioxide to hydrocarbons, such as methanol and methane".

Herein we learn that, just days ago, our United States Government officially confirmed that the King Abdulaziz City for Science and Technology and the King Fahd University of Petroleum and Minerals, in one of the pivotal and leading nations of OPEC, had indeed developed the technology to use and consume Carbon Dioxide as the key and essential ingredient in the efficient making of substitute natural gas Methane and fuel alcohol Methanol.

Comment follows and is inserted within excerpts from the initial link in this dispatch to:

"United States Patent 9,109,293 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide

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

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 electrocatalyst is prepared by dissolving copper nitrate trihydrate in deionized water to form a salt solution. Carbon 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 deionized water, either iron nitrate monohydrate, ruthenium chloride or palladium chloride may also be dissolved in the deionized water to form the salt solution.

(At this point in full Disclosures of issued United States Patents, applicable prior art is cited by the inventors, documenting the foundations upon which their innovations were based. Among the earlier inventions cited by the Saudi Arabian scientists herein is one about which we've previously reported, as in:

Chicago Electricity-driven CO2 and Hydrogen to Hydrocarbons | Research & Development | News; concerning: "United States Patent 4,959,131 - Gas Phase CO2 Reduction to Hydrocarbons; Date: September, 1990; Inventors: Ronald Cook and Anthony Sammells, IL; Assignee: Gas Research Institute, Chicago; Abstract: A process and apparatus for gas phase electrochemical reduction of CO2 and/or CO to hydrocarbons at ambient temperatures. The process is carried out by passing an electrical current between a cathode in contact with one side of a hydrogen ion conducting solid polymer electrolyte and an anode in ionic communication with the opposite side of the solid polymer electrolyte. In one embodiment, the anode material may be in contact with the opposite side of the hydrogen ion conducting solid polymer electrolyte, and in another embodiment, an anode may be separated from the opposite side of the solid polymer electrolyte by an aqueous inorganic salt solution. At least one of CO2 and CO are passed in contact with the cathode and hydrogen ions passing through the solid polymer electrolyte reduce at least a portion of the CO2 and CO to gaseous hydrocarbon products such as CH4 (Methane) and C2H4 ("Ethylene", aka "ethene"; a colorless flammable gas) at the solid polymer electrolyte/cathode interface".)

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 carbon 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 comprising copper material supported on the carbon nanotubes; cooling the solution to room temperature; removing the electrocatalyst from the solution by centrifuging the solution to separate the electrocatalyst out of the solution; washing and drying the electrocatalyst at a temperature of about 110.C; and calcining the washed and dried electrocatalyst at a temperature of about 450.C for about four hours in an argon gas flow.

(The remaining Claims specify in more detail how the catalyst is to be made. That's not of much interest to us here, but the point of it all is: Saudi Arabia knows how to make "an electorcatalyst for electrochemical conversion of carbon dioxide". Why we should actually care is made clear further on in the Disclosure, as in excerpts immediately following.)

Background and Field: 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.

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 eleetrocatalytic 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 the 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.

Summary: The electrocatalyst for the electrochemical conversion of carbon dioxide to hydrocarbons, such as methanol and methane, includes a copper material supported on carbon nanotubes."

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We haven't reproduced any of the illustrated examples provided by the Saudi's which demonstrate that CO2 can be converted into "methanol and methane", using the catalyst described herein, at voltages in the range of 1.5 to 2.5 V, a level that could be achieved by otherwise low-grade and unreliable, so-called "renewable", energy sources, such as photovoltaic arrays, and at "relatively low temperatures and in the range of atmospheric pressure".

This would, it seems clear, be an energy-efficient process for recycling CO2 into "hydrocarbons". 

The value of substitute natural gas Methane, as can be made herein by the Saudi's from Carbon Dioxide should be obvious to anyone who's been closely following the shale gas tulip-mania in the press. As it unfolds, shale gas will no doubt prove to be a rapidly-depleting resource with economically recoverable reserves far below what published estimates of "total" reserves have led the general public to believe.

Concerning the Methanol, which can be made herein by Saudi Arabia from Carbon Dioxide, we remind you that, as seen for only one example in our report of:

ExxonMobil "Clean Gasoline from Coal" | Research & Development | News; concerning the ExxonMobil publication:"Methanol to Gasoline (MTG): Production of Clean Gasoline from Coal, So Advanced, Yet So Simple", which says, in part: "There are two commercially demonstrated routes for converting coal to transportation fuels through gasification ... . The first is the widely known Fischer-Tropsch process, discovered in the 1920’s. It has been commercially practiced in several different forms to produce fuels from either coal or natural gas. Less known, is another commercially proven alternative for converting coal to gasoline through methanol. ExxonMobil Research and Engineering Company’s (EMRE) Methanol-to-Gasoline (MTG) process converts coal to high quality clean gasoline when coupled with commercially proven coal gasification and methanol synthesis technology";

Methanol, no matter which of our natural resources, whether Coal or, as herein, Carbon Dioxide, we make it from, can be directly and efficiently converted into Gasoline via known and established processes.

And, there is yet another shoe to drop in this saga. As seen in another of our reports:

King Fahd and King Abdulaziz CO2 to Hydrocarbons | Research & Development | News; concerning: "United States Patent Application 2014174916 - Catalytic Composition for the Electrochemical Reduction of Carbon Dioxide; 2014; Inventors: Saleem Ur Rahman, et. al., Saudi Arabia; Assignee: King Fahd University of Petroleum and King Abdulaziz City for Science and Technology; Abstract: The catalytic composition for the electrochemical reduction of carbon dioxide is a metal oxide supported by multi-walled carbon nanotubes. The metal oxide may be nickel oxide (NiO) or tin dioxide (SnO2)";

the same team of Saudi Arabian institutions responsible for the development of the technology of our subject herein, "United States Patent 9,109,293 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide", which relies primarily on the metals "copper, copper and ruthenium, copper and iron, or copper and palladium supported on the carbon nanotubes" to effect the efficient "electrochemical conversion of carbon dioxide to hydrocarbons", have developed closely similar CO2 catalytic conversion technology based on the readily-available and definitely non-precious metals Nickel and Tin.

Clearly, OPEC are positioning themselves to remain as key suppliers of hydrocarbon fuels to the world market, even as their natural petroleum reserves are used up, by making those hydrocarbon fuels out of Carbon Dioxide - the very stuff co-produced during our economically essential generation of abundant and reliable electric power from Coal which so many folks seem to find so objectionable, some of which folks we, here, are now convinced are motivated by impulses more economic than altruistic.

In any case, it is demonstrated again herein, as recently confirmed by the United States Government itself, that Carbon Dioxide, as we might conveniently harvest even from the atmosphere itself, is a valuable raw material resource which can be harvested and then be efficiently converted into valuable hydrocarbon fuels, such as substitute natural gas Methane and fuel alcohol Methanol.

Has anyone yet put a big old pot of Coal Country coffee on to brew? It is way past time we all woke up.


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