Method and means for hydrocarbon synthesis
The information we enclose in this dispatch will, no doubt, seem to be just more tedious repetition of facts we have, from many other sources, already established:
Carbon Dioxide can be reacted, "reformed", with Methane, with or without, depending upon the final product mix desired, the inclusion of other raw materials such as Oxygen and Steam, and be made, through such reforming reactions, to generate a synthesis gas, or "syngas", blend of Hydrogen and Carbon Monoxide suitable for subsequent Fischer-Tropsch, and related, catalytic chemical condensation into hydrocarbons.
The United States petroleum industry has known that to be true for quite a long time, as we have documented in reports such as:
1939 CO2 + CH4 = Hydrocarbons | Research & Development; concerning: "US Patent 2,180,672 - Process for Converting Gaseous Hydrocarbons; 1939; Phillips Petroleum, Oklahoma; Abstract: This invention relates to processes for the conversion of normally gaseous hydrocarbons into organic products ... and more specifically to the conversion of methane (into) hydrocarbons suitable for motor fuel ... by reacting (it) with oxides of carbon (including) carbon dioxide, monoxide or their mixtures; and:
Standard Oil 1947 Coal & CO2 to Gasoline | Research & Development; wherein we provided details of the: "US Patent 2,417,164 - Hydrocarbon Synthesis; 1947; Standard Oil Company, Chicago; Abstract: This invention relates to hydrocarbon synthesis and it pertains more particularly to an improved process and means for producing normally liquid hydrocarbons from carbon monoxide and hydrogen (which) can be (produced from, in addition to Coal) ... methane ... by reacting (it with) carbon dioxide and steam."
Such technologies are, from our point of view, now taking on an even greater significance, since some very recent developments in the art and science of Carbon Dioxide recycling actually lead to the co-production of Methane as one of the end products.
For instance, as thoroughly explained and clearly illustrated in:
USDOE $2.00 Gasoline from Carbon Dioxide | Research & Development; concerning: "Fuels from Microalgae: Technology Status, Potential, and Research Requirements; USDOE; 1986";
not only can "bio-reactors" containing specific types of Algae be fed effluent Carbon Dioxide and then produce, through their normal metabolism, "lipids", which can then be extracted and converted into, as the USDOE specifies in the text, and clearly demonstrates through illustrations, such as seen on document page 77, electronic file page 90, Figure 4-4, "Fuel Gas, Diesel, LPG and Gasoline"; but, as also explained in the text and illustrated in the same Figure 4-4, the cellular debris of the CO2-nourished algae, after their lipids have been extracted, can be processed in a "bio-reactor", where the organic residue is digested by bacteria which excrete both Carbon Dioxide and Methane as a result of their metabolism.
More on such biological production of both Methane and Carbon Dioxide from organic wastes, as specified by the USDOE, can be learned via:
Anaerobic digestion - Wikipedia, the free encyclopedia; wherein we're informed that: "Anaerobic digestion is a series of processes in which microorganisms break down biodegradable material in the absence of oxygen ... to manage waste and/or to release energy. The process produces a biogas, consisting of methane and carbon dioxide."
In our report of the USDOE technology, we suggested that the minor amount of CO2 co-produced with the Methane could simply be added back into industrial effluent Carbon Dioxide being fed to the Algae, and the Methane directed into a process such as exemplified by those in the reports we cited above, concerning: "United States Patent 2,180,672 - Process for Converting Gaseous Hydrocarbons" and "United States Patent 2,417,164 - Hydrocarbon Synthesis", with the Carbon Dioxide needed for reaction with the Methane being recovered from yet another industrial emitter of the gas.
In any case, with apologies for the over-long introduction, we wanted herein to again affirm that both the petroleum industry and our own United States Government have indeed known, since the WWII era, that Carbon Dioxide can be so reacted with Methane, and be made through those reactions to form a blend of Carbon Monoxide and Hydrogen "syngas" suitable for subsequent catalytic condensation into liquid hydrocarbon fuels.
Comment, with additional links and excerpts, follows excerpts from the initial link in this dispatch to:
"United States Patent 2,460,508 - Method and Means for Hydrocarbon Synthesis
Date: February, 1949
Inventor: Everett Johnson, Illinois
Assignee: Standard Oil Company, Chicago
Abstract: This invention relates to the synthesis of hydrocarbons having more than one carbon atom in the molecule and it pertains more particularly to an improved method and means for producing normally liquid hydrocarbons by reacting hydrogen and carbon monoxide over catalysts ... .
More specifically it relates to hydrocarbon synthesis with methane as the raw material.
When methane ... is reformed by direct combustion with oxygen, a certain amount of excess heat is available ... .
Carbon dioxide can be incorporated in the feed gas in quantities sufficient to absorb excess heat by reacting it endothermically with a portion of the (methane).
The incorporation of carbon dioxide in the feed gas not only simplifies the design of the reformer by making the operation thermally balanced, but also increases the overall carbon efficiency of the process.
Consequently from the standpoint of thermal and carbon efficiency it is desirable to feed to the reforming operation a gas comprising methane, oxygen and carbon dioxide.
(By the way, in case you've forgotten what you learned in your high school Biology 1 class, the Algae, as in our above reference to our USDOE's "Fuels from Microalgae" report, will, in the course of their usual metabolism, while photosynthetically converting industrial effluent CO2 into such presumably delightful things as Gasoline and Diesel, will also be burping up a fair amount of molecular Oxygen, as required by Standard Oil's Carbon Dioxide recycling process.
We must further interrupt to explain that Standard Oil goes on at great length about the proportions of the components in what they refer to as the "make gas", derived from the reactions between CH4 and CO2, and how such gas reacts differently, over different types of catalysts, primarily those from the Iron Group metals. Should you examine the full document, just keep in mind that the "make gas" is actually synthesis gas, and, it is made, as Standard Oil specifies, from "methane, oxygen and carbon dioxide", with, in some examples, a little H2O tossed into the salad. But, they suggest other intriguing options for obtaining their "make gas", as well, as follows.)
The hydrogen-carbon monoxide mixture can be suitably obtained from ... methane ... as the raw material.
However, my invention is not limited to the source of the carbon monoxide-hydrogen mixture and may be obtained for example from coal .. or other carbonaceous materials.
The basic equations for the gas reforming operation using methane may be somewhat as follows:
CH4 + CO2 = 2CO + 2H2 (and) CH4 + 0.5O2 = CO + 2H2.
The proportions of carbon dioxide and steam and/or oxygen containing gas can in any case be so adjusted to give the desired make gas.
(We must further interrupt to note that Standard Oil suggests the "oxygenated compounds", i.e., Alcohols, generated as co-products, along with hydrocarbons, from the catalytic condensation of the "make gas", be recycled back into the syngas generation stage, where it, too, will react with the CH4 and CO2.
They also specify, and we regret the need to over-summarize, that both some of the needed Oxygen and some of the Hydrogen is to be supplied by Steam originating, as well, from the syngas catalytic condensation, since it will be at a very high temperature, and will thus afford energy economies in it's reactions with Methane and Carbon Dioxide.
The Disclosure then goes on in commendable detail to explain how parallel catalyst systems, again using just Iron Group metals, are employed to fully convert all of the Carbon content of their final "make gas" into hydrocarbons; as they summarize, following)
From the above detailed description, it will be apparent that we have attained the objects of our invention and have provided an improved process employing parallel units to effect the optimum conversion of hydrogen and carbon monoxide to hydrocarbon products ... having high proportions of olefins.
(Note that, not only are hydrocarbons useful as fuel produced in this process, but, so are "olefins". For an explanation of how useful they might be, have a look at:
Olefins | Petrochemicals Production | Refinery Petrochemicals | Olefins Production | Olefins Process | KBR: A Global Engineeri; wherein a major petroleum industry company, Kellogg, Brown & Root, who have several times figured in our reports, tells us that: "Olefins are in a class of hydrocarbons with a single double bond and a chemical formula of CnH2n. The two most important olefins are ethylene and propylene, as they form the backbone of the petrochemicals market."
So, not only can we get hydrocarbon fuels by starting with Methane and Carbon Dioxide, but, plastics manufacturing raw materials, as well.)
Claims: The process of synthesizing hydrocarbons from hydrogen and carbon monoxide mixtures produced by converting hydrocarbons (specified, as above, to be Methane) with carbon dioxide and oxygen in a substantially thermally balanced reaction."
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And, of course, Standard Oil would have been aware, in 1949, that the Methane needed, to react with Carbon Dioxide, to make the "hydrogen and carbon monoxide mixtures" from which "hydrocarbons" could be so efficiently synthesized, could itself be made, as seen in:
CO2 Solution Wins Nobel Prize - in 1912 | Research & Development; as confirmed in 1912 by Europe's Nobel Prize Committee, from Carbon Dioxide.
Further, not only has that fact since been confirmed many times, and better ways found to accomplish the conversion of CO2 into Methane, as evidenced by:
NASA Recycles CO2 to Methane at Room Temp | Research & Development | News; concerning the: "Electrocatalytic Reduction of Carbon Dioxide to Methane; Lyndon B. Johnson Space Center; 2008";
but, so has Standard Oil's basic premise of our subject herein, "US Patent 2,460,508 - Method and Means for Hydrocarbon Synthesis", as much later confirmed by West Virginia University, in:
WVU CO2 + CH4 = Hydrocarbon Syngas | Research & Development; wherein is detailed: "New Catalysts for Syngas Production from Carbon Dioxide and Methane; Mahesh V. Iyer; West Virginia University; 2001;
which describes technology very similar to that disclosed by Standard Oil, in United States Patent 2,460,508, for reacting Carbon Dioxide with Methane, to form a blend of Carbon Monoxide and Hydrogen, suitable, as WVU confirms by their approval of Iyer's full thesis, which clearly states that such "Syngas" is quite suitable for the synthesis of "long-chain hydrocarbons and ... alcohols".