In an earlier dispatch, now accessible via:
West Virginia Coal Association | Phillips CO2 + Coal + H2O = Methane | Research & Development;
we made report of:
"US Patent 4,011,058 - Production of Substitute Natural Gas from Gasification of Coal Char; 1977; Inventors: Marvin Johnson, et. al.; Assignee: Phillips Petroleum Company, OK; Abstract: A carbonaceous material is converted to a fuel gas which is fungible with natural gas by a combination of steps comprising gasifying the carbonaceous material in the presence of air and carbon dioxide, purifying the effluent stream and separating carbon monoxide therefore, catalytically reacting steam with the separated carbon monoxide and recovering a methane-rich product gas";
wherein it was confirmed yet again that Carbon Dioxide can be recycled through reactions with hot Coal, and other "carbonaceous material", with the subsequent production of the chemically reactive and very useful Carbon Monoxide.
We've previously documented how valuable such Carbon Monoxide, as derived from such reactions between Carbon Dioxide and Coal, can be, as seen, for just one example, in our report of:
Standard Oil Carbon Monoxide + Water = Gasoline | Research & Development; concerning: "United States Patent 4,559,363 - Process for Reacting Carbon Monoxide and Water; 1985; Abstract: A process for reacting carbon monoxide and water in the presence of a cadmium-containing catalyst ... for the direct production of gasoline."
However, as Phillips Petroleum noted in their Disclosure of "United States Patent 4,011,058 - Production of Substitute Natural Gas from Gasification of Coal Char", Carbon Monoxide, as they made it from Coal and Carbon Dioxide, can also be "catalytically" reacted with "steam" to effect the synthesis of "a methane-rich product gas".
And, herein, we document just how Phillips, and their Carbon conversion scientist, Marvin Johnson, envisaged converting that CO2-derived Carbon Monoxide into Methane; as seen, with comment inserted and appended, in excerpts from the initial link in this dispatch to:
"United States Patent 4,071,331 - Producing Methane from Carbon Monoxide and Steam
Date: January, 1978
Inventors: Marvin Johnson and Gerhard Nowack, OK
Assignee: Phillips Petroleum Company, Bartlesville, OK
Abstract: A catalyst consisting essentially of nickel, a promoter selected from the group consisting of barium and uranium and a calcium phosphate support having a Ca:P atomic ratio in the range of 1.4:1 to 2.3:1, is formed by impregnating a calcium phosphate gel with suitable compounds of nickel and either barium or uranium. The resulting catalysts are useful for reacting carbon monoxide and steam and in steam reforming processes for producing methane.
(We know that Uranium sounds nasty; but, depending on it's form, it needn't be overly radioactive or dangerous. Unless it's artificially "enriched", and converted into a more radioactive isotope, the radiation it emits is the weak "alpha" type, which is generally regarded as being harmless to humans. In fact, Uranium was used for at least a full century as a component of consumer products, including tableware and drinking glasses, made of what is called commonly "Depression Glass", or, more accurately, "Uranium Glass". For more info, see:
Uranium - Wikipedia, the free encyclopedia; and: Uranium glass - Wikipedia, the free encyclopedia.
Further, although it isn't really clear to us, though someone better informed and educated could likely make the distinction, it appears that only very small amounts of Uranium, as little as "2%" of total catalyst and promoter composition, are actually needed, and, that the Methane production reaction can proceed satisfactorily if catalyzed with Nickel "promoted" only, or primarily, with the less onerous "barium". - JtM)
Claims: A process for the conversion of a feed consisting essentially of carbon monoxide and steam to a gas containing methane and carbon dioxide which comprises contacting carbon monoxide and steam at an elevated temperature with a catalyst composition consisting essentially of nickel, a promoter selected from the group consisting of barium and uranium, combined oxygen and a calcium phosphate support having a Ca:P atomic ratio in the range of 1.4:1 to 2.3:1, wherein the components are present in approximate amounts as (specified).
The process ... wherein said conversion is conducted at a temperature in the approximate range of 300 to 1000F, at a pressure in the approximate range of 0 to 2000 psig, ... and a carbon monoxide to steam mole ratio in the approximate range of 2:1 to 1:5.
The process ... wherein said catalyst consists essentially of from about 5 to about 35 weight percent calcium, from about 2 to about 20 weight percent phosphorus, from about 10 to about 50 weight percent nickel and from about 2 to about 40 weight percent uranium.
Description: Utility companies which distribute gas for household or other use have an increasingly acute need for an economical means of supplying gas during peak-load periods. During cold weather, for example, demand may be double or triple the volume used on a mild day. In many instances, the peak-load demand is met by adding propane-air mixtures to the gas. Because the quantity of propane-air that can be blended is limited, there is a need for an economical process that can be used to supply peak-load demand.
Methanation by steam reforming carbon monoxide is ... a well known process. The process produces a mixture of methane, carbon monoxide, carbon dioxide and hydrogen. Various catalysts are known for such methanation processes, however, many such catalysts produce methane containing an undesirable amount of carbon monoxide which can be difficult to separate. Further, carbon monoxide in admixture with methane is highly undesirable because of the high toxicity of the carbon monoxide in the event leaks occur in supply lines or in storage containers.
It is an object of this invention to provide a new and improved catalyst useful for steam reforming (and) a process for methanation by steam reforming carbon monoxide.
In accordance with the present invention there is provided a catalyst composition consisting essentially of nickel, a promoter metal selected from the group consisting of barium and uranium, combined oxygen and a calcium phosphate support having a Ca:P atomic ratio in the range of 1.4:1 to 2.3:1. The catalyst compositions of this invention contain calcium, phosphorus, nickel and barium or uranium in the (relative amounts specified).
It is presently preferred that the methanation process be conducted at a temperature in the approximate range of 400 - 800F ... at a pressure in the approximate range of 100 to 1,000 psig ... and a carbon monoxide to steam mole ratio in the approximate range of 1:1 to 1:3.
It is presently preferred that the nickel on calcium phosphate catalyst used for methanation by reaction of CO and steam be promoted with uranium.
The carbon dioxide produced in ... the above processes can be removed by conventional methods, such as by absorption in an amine solution."
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And, presumably, any Carbon Dioxide that is co-produced and "removed by conventional methods" can be recycled back into the process of our earlier-reported "US Patent 4,011,058 - Production of Substitute Natural Gas from Gasification of Coal Char", wherein it would, along with Coal, be converted back into more of the Carbon Monoxide required by the process of our subject herein, "US Patent 4,071,331 - Producing Methane from Carbon Monoxide and Steam".
However, although our sadly-limited capacities don't allow us to say so categorically, and someone genuinely competent should review the full Disclosure to ascertain the accuracy of our analysis, it appears from accompanying references that the amount of Carbon Dioxide co-produced would be, relative the amount of produced Methane, small.
If so, then the co-produced CO2, instead or being directed back into the process of "US Patent 4,011,058", could, instead, be combined with a portion of the Methane produced by the process of our subject herein, "United States Patent 4,071,331 - Producing Methane from Carbon Monoxide and Steam", in a process like that disclosed, for just one out of now many similar examples, in our report of:
Exxon 2010 CO2 + Methane = Liquid Hydrocarbons | Research & Development; concerning: "United States Patent 7,772,447 - Production of Liquid Hydrocarbons from Methane; 2010; Assignee: ExxonMobil; Abstract: (A) process for converting methane to liquid hydrocarbons ... (by) contacting a feed containing methane and ... H2O (and) CO2 with a (specified) catalyst under conditions effective to convert said methane to aromatic hydrocarbons";
with both the Methane and the Carbon Dioxide being together converted through such and similar reactions into "liquid hydrocarbons".
And, thus, it seems to us, that, by starting out with the process disclosed in our earlier report of "US Patent 4,011,058 - Production of Substitute Natural Gas from Gasification of Coal Char", wherein Carbon Dioxide is reacted with hot Coal to form Carbon Monoxide, and following through with the process of our subject herein, "US Patent 4,071,331 - Producing Methane from Carbon Monoxide and Steam", and, then, with that, or similar, of the Exxon process of "US Patent 7,772,447 - Production of Liquid Hydrocarbons from Methane", it would seem possible to achieve a net production of both Methane and "liquid hydrocarbons", by starting out only with, as raw materials, "air and carbon dioxide", "Steam", and Coal.
Think we could scrape any of that stuff together somewhere in West Virginia, Pennsylvania, or any of the other parts of US Coal Country?