As in our recent post: 1940 CO2 + H2O + CH4 = Hydrocarbon Syngas | Research & Development | News; wherein is detailed: "US Patent 2,198,553 - Making a Synthesis Gas Mixture of Carbon Monoxide and Hydrogen; 1940; George Roberts; Assignee: The M.W. Kellogg Company, NY"; we have, as certified therein by the United States Patent office, known since the early days of WWII that we can "tri-reform" Carbon Dioxide, in a fashion very similar to that explained more lately by scientists, such as Chunsan Song and Craig Grimes, at Penn State University, and thereby generate a synthesis gas suitable for catalytic condensation into liquid hydrocarbon fuels.
Herein, we see that the above-named inventor of USP 2,198,553 continued his work, subsequent and relative to award of that patent, and, later in WWII, M.W. Kellogg, now a component of the Texas-based petroleum industry services company, Kellogg, Brown & Root, was assigned the rights to yet another patent, for equipment and physical plant related to the recycling of Carbon Dioxide through such reactions with Methane and Water vapor.
Comments, and a few additional reference links, follow excerpts from:
"United States Patent 2,355,753 - Catalytic Apparatus
Date: August, 1944
Inventor: George Roberts, NJ
Assignee: The M.W. Kellogg Company, NJ
Abstract: The present invention relates generally to improvements in apparatus for effecting catalytic reactions ... of an endothermic character.
My invention is especially well exemplified in it's application to the production of a synthesis gas adapted for use in the synthesis of various organic compounds, as for example, the production of a mixture of carbon monoxide and hydrogen for use in the production of hydrocarbons in accordance with the Fischer-Tropsch synthesis reaction.
(Such " Fischer-Tropsch synthesis" was, we remind you, developed early in the last century to synthesize liquid hydrocarbon fuels out of "syngas" generated from Coal.)
A synthesis gas suitable for use in this (Fischer-Tropsch) reaction may be prepared by the interaction of methane with carbon dioxide, or with steam, or with a mixture of carbon dioxide and steam ... .
All the (necessary) reactions are endothermic ... and require the maintenance of an elevated temperature ... .
(The needed temperatures specified are quite high - affording, we would think, the environmentalists among us an opportunity to prove the worth of such things as concentrated solar energy. We remind you, as we will in the future further document, that, as in earlier of our reports, the nation of Iceland is constructing a
Carbon Dioxide recycling factory which will utilize geothermal energy to drive the processes.)
Various known types of catalytic material may be employed for this reaction, as for example, nickel deposited on clays of high alumina content ... .
(Which sounds a lot like "standard" Fischer-Tropsch catalysis, as far as the Nickel is concerned; and, specification of "clays of high alumina content", for the catalyst support, could relate this technology to later developments, such as ExxonMobil's "MTG"(r) process for converting Coal-derived Methanol into Gasoline, wherein one key to the process is use of the "ZSM-5" catalyst, which is a synthetic or natural - we're uncertain - "zeolite"; a type of mineral, which, as we've been informed by parties we believe to be knowledgeable, could be described as an aluminum-containing clay.)
The operation of the device may be illustrated by its application to the manufacture of a synthesis gas mixture containing a 2:1 ratio of hydrogen to carbon monoxide, from a mixture of methane, carbon dioxide and steam according to the equation: 3CH4 + CO2 + 2H2O = 4CO + 8H2.
(Which we believe, based on our understanding of prior references, to be an advantageous CO-H2 ratio for the further catalytic condensation of such synthesis gas, as via, for just one example, as identified herein by Kellogg, the Fischer-Tropsch process, into a useful range of liquid hydrocarbons.)
(It) will be apparent that I have accomplished the objects of my invention in providing an improved type of apparatus for carrying out endothermic reactions such as the manufacture of synthesis gas."
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We end our excerpts here since the bulk of the full Disclosure is devoted to specifying the catalyst, and catalyst structure, and to explaining how and why it works so well in the process of reacting "methane with carbon dioxide, or with steam, or with a mixture of carbon dioxide and steam"; and, thus breaking Carbon Dioxide, Methane and Water down into a liquid hydrocarbon synthesis gas mixture of Carbon Monoxide and Hydrogen; a gas composition very suitable, as specifically stated by Kellogg, "for use in the production of hydrocarbons in accordance with the Fischer-Tropsch synthesis reaction".
Since Methane can be utilized herein for the recycling of Carbon Dioxide, we remind you that we can synthesize that needed Methane either from Coal, as, for just one example, in:
1910 Methane & Hydrogen from Coal | Research & Development | News; wherein is disclosed:
"United States Patent 956,734 - Manufacturing Mixtures of Methane and Hydrogen; 1910; Paul Sabatier, France; The present invention relates to a process for the manufacture of Methane or of mixtures of Methane and Hydrogen ... by passing water gas over heated nickel. ... The water gas is manufactured (by passing) super heated steam ... through coke (and/or) anthracite, wood, charcoal";
or, from Carbon Dioxide, as in:
NASA Recycles CO2 to Methane at Room Temp | Research & Development | News; which reports that:
"Electrocatalytic Reduction of Carbon Dioxide to Methane; 2008; A room-temperature electrocatalytic process that effects the overall chemical reaction CO2 + 2H2O → CH4 + 2O2 has been investigated" a process which could "have potential utility in terrestrial applications in which either or both of the methane and oxygen produced might be utilized."
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We call your attention to the fact that Paul Sabatier's 1910 technology, starting with Coal, generates not only the Methane that would be required by Kellogg's WWII-era Carbon Dioxide recycling technology, but also Hydrogen, which could, among other things, be used in the process which won Sabatier the 1912 Nobel Prize in Chemistry, and which NASA is readying for use, as we've several times documented, to make rocket fuel on the planet Mars, wherein CO2 is reacted with Hydrogen and made thereby to form more Methane; which could, as herein, via the process USP 2,355,753, then be further reacted with even more Carbon Dioxide, to, ultimately, synthesize other needed and valuable hydrocarbons.