We've previously documented, in several reports, the Carbon conversion expertise of the, apparently former, Exxon scientist Rocco Fiato, regarding primarily the science he helped to develop, while at Exxon Research and Engineering Company, for the productive chemical recycling of Carbon Dioxide.
We mentioned him recently in a dispatch concerning the New York City-based Carbon Dioxide recycling enterprise, Global Thermostat, LLC; who claim their "patent-pending technology uses low-cost left over process heat as energy for the capture of CO2 from the atmosphere (and, it) can be installed at new or legacy power plants, cement smelters (and) refineries".
In that report, as accessible via:
New York City Reclaims and Recycles Carbon Dioxide | Research & Development;
we included, since Rocco Fiato is named by Global Thermostat to be a member of their advisory team, links to two of our earlier dispatches to the West Virginia Coal Association, concerning some of the Carbon Dioxide recycling technology that had been established by him during his career at Exxon, as in:
Exxon Recycles CO2 to Gas and Liquids | Research & Development; concerning: "United States Patent 5,140,049 - Method for Producing Olefins from H2 and CO2; 1992; Inventor: Rocco Fiato, et. al., NJ; Assignee: Exxon Research and Engineering Company, NJ; This invention relates to a process for producing C2 -C20 olefins from a feed stream consisting of H2 and CO2 using an iron-carbide based catalyst"; and:
Exxon Recycles CO2 | Research & Development; concerning the report: "Iron catalyzed CO2 hydrogenation to liquid hydrocarbons; Rocco A. Fiato, E. Iglesia, G.W. Rice and S.L. Soled;
Exxon Research and Engineering Company; (Abstract:) Many of the catalysts which are useful in Fischer-Tropsch synthesis are also capable of catalyzing the hydrogenation of CO2 to hydrocarbons. Our structure-function studies have shown that it is possible to control the selectivity of CO2 hydrogenation by specific iron-based catalysts to generate yields of C5 + hydrocarbons that are comparable to those produced with conventional CO based feedstocks".
Herein, we learn that Fiato, while at Exxon, and in partnership with a now very intriguing Exxon colleague, also worked on improving the conversion of a mixture of Hydrogen and Carbon Monoxide into liquid hydrocarbons.
Sadly, a little forewarning is necessary:
Like some other expositions of Big Oil technology for the conversion of Coal into more versatile Hydrocarbons, the full Disclosure of the US Patent which is the focus of this dispatch manages to avoid any use, at all, of the dirty, four-letter word "Coal".
Fiato and his colleague disclose only the treatment of "mixtures of CO and H2".
But, they do, obviously, name the esteemed "Fischer" and "Tropsch" in the title of their work, and, as in:
Volkswagen Group - Fischer-Tropsch Synthesis; wherein we're told, that the: "Fischer-Tropsch synthesis (FT) is a technical process for converting synthesis gas into liquid and solid paraffinic hydrocarbons. It was developed by German chemists Franz Fischer and Hans Tropsch and patented in 1925. The liquid hydrocarbons are used as fuels, the solid hydrocarbons are highly pure waxes that are used as raw materials for the chemical or pharmaceutical industry. Local hard coal was used as the raw material";
we see that Fischer and Tropsch themselves used "coal ... as the raw material" from which they made their own synthesis gas blends.
And, again, Exxon does herein center on the use only of Carbon Monoxide and Hydrogen, a "synthesis gas", which, as affirmed in:
synthesis gas - definition of synthesis gas by the Free Online Dictionary, Thesaurus and Encyclopedia.; is a "mixture of gases" that can be "produced by controlled combustion of coal in the presence of water vapor".
In comment appended to excerpts from the initial link in this dispatch, we explain in passing why the focus herein is on the use of Hydrogen and Carbon Monoxide blends only, to the exclusion of Carbon Dioxide:
"United States Patent 4,689,313 - Iron on Titania Fischer-Tropsch Catalyst
Date: August, 1987
Inventors: Rocco Fiato and Edwin L. Kugler, NJ
Assignee: Exxon Research and Engineering Company, NJ
(And, here, we must interrupt in order to explain that the above Edwin L. Kugler, though in 1987 an employee of Exxon, is, now, as seen in:
Chemical Engineering - Dr. Edwin L. Kugler; concerning: "West Virginia University, College of Engineering and Mineral Resources, Department of Chemical Engineering, Faculty and Staff; Dr. Kugler's research interests are focused on producing liquid and gaseous fuels from coal and biomass using heterogeneous catalysis, reaction engineering and materials science. His current interests in catalysis involve producing liquid fuels from CO and H2 mixtures using Fischer-Tropsch and water-gas-shift reactions. Dr. Kugler is recognized nationally for his work in catalysis and is supported by the Department of Energy";
ensconced, happily we hope, in one of West Virginia's very own ivory towers that adorn the eastern bank of the northern reaches of the Monongahela River.)
Abstract: A catalyst useful for producing substantially C2 + alkane hydrocarbons from mixtures of CO and H2 which comprises a mixture of iron carbide and ilmenite supported on titania wherein the ratio of the iron present in the supported iron carbide and ilmenite (is in a specified range).
(Note: The "ilmenite" is more informatively known as "iron titanium oxide", FeTiO3, and, more informally, but also informatively, as "titanic iron ore". An exotic mix of gold dust and rose oil it ain't. The "titania" is just titanium dioxide, and it can likely be extracted from the "ilmenite". And, "iron carbide", we shouldn't have to explain, can be made, in the right conditions, out of some red-hot Iron - - which we could extract from the "ilmenite" as well, while we're making the "titania" - - and, a little Coal.)
Claims: A catalyst composition a consisting essentially of catalytic components supported on titania, said catalytic components being selected from the group consisting of a mixture of iron carbide and ilmenite and a mixture of iron carbide and ilmenite containing at least one alkali metal promoter (according to specifications).
A process for forming a catalyst comprising a mixture of ilmenite and iron carbide supported on titania useful for producing substantially alkane hydrocarbons from mixtures of CO and H2 ... .
(The "alkane hydrocarbons" could, and likely would, as can be seen in:
Organic Chemistry:; include the gases: methane, ethane, propane and butane; and, the liquids: pentane, hexane, heptane, and the more-familiar octane.
Heavier, waxy solid hydrocarbons can also be produced.
As we have previously documented, and as we will in future dispatches report, Fischer-Tropsch reaction conditions can be "adjusted", so as to influence the product mix towards desired end products.
But, note that Methane is one of the compounds that will result, and, remember that, even though the Fischer-Tropsch reaction will itself generate a little co-product Carbon Dioxide, as seen in:
WVU CO2 + CH4 = Hydrocarbon Syngas | Research & Development | News; concerning: "New Catalysts for Syngas Production from Carbon Dioxide and Methane; Mahesh V. Iyer; College of Engineering and Mineral Resources at West Virginia University: Edwin L. Kugler, Ph.D., Chair; This project has demonstrated the performance of a cobalt tungsten carbide material as a catalyst precursor for methane dry reforming with carbon dioxide to produce synthesis gas";
one of the co-inventors herein, the esteemed Dr. Kugler, confirms the findings by one of his WVU students that the by-product Carbon Dioxide can be reacted with some of the product Methane, with both being converted through such reaction into even more of the "mixtures of CO and H2" that are converted into a broader range of "alkane hydrocarbons" through the action of the catalyst described herein by our subject, Exxon's "United States Patent 4,689,313 - Iron on Titania Fischer-Tropsch Catalyst".)
Background and Field: This invention relates to a Fischer-Tropsch catalyst comprising a mixture of iron carbide and ilmenite supported on titania. More particularly, this invention relates to a catalyst for producing substantially alkane hydrocarbons from mixtures of CO and H2 comprising a mixture of iron carbide and ilmenite supported on titania.
It has now been discovered that substantially C2 + alkane hydrocarbons can be produced from mixtures of CO and H2 using a catalyst comprising iron supported on titania.
By substantial alkane hydrocarbons is meant that more than about 50 wt.% of the hydrocarbon products, including methane, are alkane C2.+ hydrocarbons. In a preferred embodiment the catalyst will be pretreated with CO at elevated temperature prior to use."
---------------------
And, if, as immediately above, we do need just some plain old extra "CO", Carbon Monoxide, to "pretreat" the catalyst, then, as in:
More Pre-WWII CO2 Recycling | Research & Development; concerning: "US Patent 2,128,262 - Carbon Monoxide Manufacture; 1938; Semet-
we can make that Carbon Monoxide rather simply by passing Carbon Dioxide, recovered from whatever handy source, through red-hot Coal.
We noted in introductory comments that our subject, "United States Patent 4,689,313", is focused only on the conversion of Hydrogen and Carbon Monoxide synthesis gas blends, to the exclusion of Carbon Dioxide; even though Carbon Dioxide will react with Hydrogen under closely similar sets of conditions and catalysts.
The reason, as has been suggested to us, and as we will attempt to document in coming reports, is that the inclusion of Carbon Dioxide in the synthesis gas mix leads - - in a subsidiary reaction within the overall Fischer-Tropsch synthesis, which is very similar to the Nobel Prize-winning Sabatier process described in:
Sabatier reaction - Wikipedia, the free encyclopedia; "The Sabatier reaction ... involves the reaction of hydrogen with carbon dioxide (according to the equation): CO2 + 4H2 = CH4 + 2H2O";
and, which consumes available Hydrogen - - to the formation of Methane preferentially to "higher", or molecularly more complex, and presumably more desirable, liquid "alkane" hydrocarbons, such as the above-noted "octane".
In any case, we have herein further confirmation of the fact, that:
We can make any and all of the hydrocarbons we might want or need, anything at all that we're currently importing from anyone, friend or foe, by simply digging up a little bit more of our abundant Coal.