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Amoco 1997 Methane to Hydrocarbon Syngas

United States Patent: 5591238

Last December, we made report of Carbon Dioxide recycling technology that had been developed by the once well-known Amoco Corporation; which report is now accessible on the West Virginia Coal Association's web site via the link:

Amoco CO2 + CH4 = Hydrocarbon Syngas | Research & Development; wherein we discussed: "United States Patent 5,614,163 - Process for Making Synthesis Gas; 1997; Assignee: Amoco Corporation; Abstract: A process is disclosed for preparing a synthesis gas comprising hydrogen and carbon monoxide by partial oxidation of hydrocarbyl compounds using ... carbon dioxide, or mixtures thereof in the presence of a catalyst comprising ... a hydrotalcite-like compound".

 

 

Methane is one specific and suitable "hydrocarbyl" compound named by Amoco in their full Disclosure to be reacted with Carbon Dioxide.

Somewhat unfortunately, that report actually duplicated in subject matter, i.e., "US Patent 5,614,163", another report we had made about six months prior.

We regret that lapse, but our own many shortcomings are actually compounded by the bewildering array of Carbon Dioxide recycling, and other Carbon conversion, US Patents that have been awarded to the Amoco scientist, Alakananda Bhattacharyya, named as the lead inventor in those earlier reports.

We have been putting some effort lately into an attempt to sort through and organize what we can find of  Bhattacharyya's published work, so that we can present it to you in more orderly fashion; and, herein, we submit a United States Patent that represents Methane conversion art, with associated Carbon Dioxide recycling implications and potentials, developed by Amoco scientists, which was somewhat precedent to that disclosed in "US Patent 5,614,163".

Our subject matter herein doesn't actually utilize Carbon Dioxide directly in it's specified process for converting Methane into a blend of Carbon Monoxide and Hydrogen, i.e., hydrocarbon synthesis gas; but, it is actually founded on and related to such technology, as it reveals in it's discussion of prior art.

It might also be helpful to keep in mind that, as seen in:

Penn State Solar CO2 + H2O = Methane | Research & Development; concerning: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; The Pennsylvania State University; 2009; Efficient solar conversion of carbon dioxide and water vapor to methane";

some attractive options for synthesizing the Methane out of Carbon Dioxide, by utilizing freely-available environmental energy, do exist.

Further, our subject utilizes in it's process some compounds that relate to the at least potential of indirect Carbon Dioxide utilization; and, it has what should by now be obvious implications for other direct Carbon Dioxide utilization processes, similar to the above-noted Penn State technology, as we emphasize in comments, inserted within and following excerpts from the initial link to:

"United States Patent 5,591,238 - Preparing Synthesis Gas Using Nickel Catalysts

Date: January, 1997

Inventor: Alakananda Bhattacharyya, et. al., Illinois

Assignee: Amoco Corporation, Chicago

(Amoco, as we've earlier reported, was acquired in 2001 by British Petroleum.)

Abstract: A method and nickel-containing catalyst are disclosed for preparing synthesis gas by the reforming of a hydrocarbyl compound using an oxygen-containing compound.

Claims: A method for preparing synthesis gas comprising feeding a gaseous or vaporizable hydrocarbyl compound and an oxygen-containing gas comprising molecular oxygen, to a suitable reaction zone containing a catalyst comprising the composition formed by heat treating (as specified) at least one hydrotalcite compound.

(The above "hydrotalcite", though seemingly unpronounceable, is something commonly mentioned in documentation of similar synthesis gas formulation technologies. We'll get around to explaining what it is in a dispatch to follow someday; but, for now, trust us: it ain't something we'll have to break the piggy bank to buy, or summon up the ghost of old Doc Einstein to make for us.)

The method ... wherein the hydrocarbyl compound is a hydrocarbon (and) wherein the hydrocarbon comprises methane.

Background and Field: This invention relates to a method for preparing synthesis gas by reacting a hydrocarbyl feed material with a source of oxygen at an elevated temperature. More particularly, this invention relates to the preparation of synthesis gas using new nickel-containing catalytic materials that are unusually resistant to deactivation. Additionally, this invention relates to new nickel-containing catalyst precursor and catalyst compositions that are useful for the production of synthesis gas and which catalysts are resistant to coke formation when used to catalyze the reaction of a hydrocarbyl compound with an oxygen-containing gas at elevated temperatures to form synthesis gas.

(Please recall that in some of our earlier reports concerning similar technology, "coke formation" on catalyst surfaces was a problem dealt with in part by adding H2O to the mix of CO2 and Methane. And, this technology is thus very similar to, perhaps directly derivative of, others established much earlier, as in:

Pittsburgh 1941 CO2 + Methane = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 2,266,989 - Manufacture of a Gas from CO2 and Methane; 1941; Assignee: Koppers Company, Pittsburgh, PA; Abstract: The present invention relates to the manufacture of gases suitable for the synthesis of higher hydrocarbons or the like, said gases containing definite volumes of carbon monoxide and hydrogen in a certain proportion, by reacting on methane ... with carbon dioxide or a mixture of carbon dioxide and steam, so that the methane ... is decomposed into hydrogen and carbon monoxide.")

Synthesis gas, a mixture of carbon monoxide (CO) and molecular hydrogen (H2), is a valuable industrial feedstock for the manufacture of a variety of useful chemicals. For example, synthesis gas can be used to prepare methanol or ... higher molecular weight alcohols or aldehydes as well as higher molecular weight hydrocarbons.

Perhaps the most common commercial source of synthesis gas is the steam reforming of coal.

Synthesis gas can also be produced by the reaction of ... methane with carbon dioxide."

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And, we'll end our excerpts right there, since the making of a hydrocarbon syngas "by the reaction of ... methane with carbon dioxide", wherein CO2 can actually serve as the "oxygen-containing compound" with which the "hydrocarbyl compound", i.e., Methane, is "reformed', is really what this is all about.

We'll note that, though not reflected in our excerpts, Amoco does specify the use of "carbonate" metal compounds as both catalysts and, we are led to conclude, co-reactants in this process. Such metal carbonates could be obtained, as we've previously documented, from devices which utilize alkali metal oxides or hydroxides to capture CO2 either from industrial exhaust gases or even the atmosphere itself.

In sum, and aside from the fact that "the most common commercial source of synthesis gas is", which might come as a big surprise to the residents of WV and PA, "the steam reforming of coal", note again that we can also manufacture "synthesis gas", which can then be catalytically condensed into "methanol" and/or "higher molecular weight hydrocarbons", through the "reaction of ... methane with carbon dioxide".

Which Methane, we are again compelled to remind you, we can, as seen in:

NASA Rocket Fuel from CO2 | Research & Development; wherein our own National Aeronautics and Space Administration tells us that: "methane can be manufactured ... via the Sabatier process: Mix some carbon dioxide (CO2) with hydrogen (H), then heat the mixture to produce CH4 and H20 -- methane and water";

make from Carbon Dioxide itself.

Or, as seen in:

Consol 1970 Coal + Steam = Methane + Syngas | Research & Development; concerning: "United States Patent 3,503,724 - Producing Mixtures of Methane, Carbon Monoxide and Hydrogen; 1970; Assignee: Consolidation Coal Company; This application relates to the production of mixtures of methane, carbon monoxide and hydrogen which are particularly suitable for the preparation of high Btu gas from carbonaceous material such as coal";

we can make the Methane, required by Amoco, via their process herein of "US Patent 5,591,238", to make a "synthesis gas" suitable for manufacturing "methanol (and) higher molecular weight hydrocarbons", as the valuable by-product of a process that makes even more such syngas "mixtures of ... carbon monoxide and hydrogen" out of some of our abundant Coal.