PROCESS FOR THE PRODUCTION OF A CARBON MONOXIDE CONTAINING GAS
As we again recently documented, in our report of:
Bayer Improves Coal + CO2 = Carbon Monoxide | Research & Development; concerning, primarily: "United States Patent 7,473,286 - Carbon Monoxide Generator; 2009; Bayer Material Science, AG, Germany; Abstract and Claims: A generator (which produces Carbon Monoxide) having a purity of greater than 96%, preferably from 97 to 98% (via a) continuous process in which carbon-containing raw materials are reacted with oxygen and carbon dioxide";
it is perfectly practical and feasible to recycle Carbon Dioxide, reclaimed from whatever source, by reacting it in a controlled fashion with "carbon-containing raw materials" such as Coal.
Such technology is so sophisticated and complete, moreover, that, as seen in:
Exxon Coal + CO2 + H2O Combo Gasification & Conversion | Research & Development; concerning: "United States Patent 4,318,712 - Catalytic Coal Gasification Process; 1982; Assignee: Exxon Research and Engineering; A process for the catalytic steam gasification of coal (designed) to promote the reaction of steam, hydrogen, carbon dioxide, or a similar gasification agent with (carbon)";
other reactants, such as Water, H2O, can be added to the Carbon Dioxide with which Coal is gasified, to influence the composition of the product gas in beneficial ways and make it more suitable for catalytic chemical condensation into liquid hydrocarbons.
Herein, we submit closely-similar Exxon-developed, or, rather, "Esso"-developed, Coal gasification technology, which was formalized fully one decade before, and can be seen as directly precedent to, that of "United States Patent 4,318,712". And, despite the title of our subject, it, too, is concerned not just with producing Carbon Monoxide, but, a blend of Carbon Monoxide and Hydrogen which could be utilized as an almost completely-formulated hydrocarbon synthesis gas.
Comment follows, and is inserted within, excerpts from the initial link in this dispatch to:
"United States Patent 3,758,673 - Production of a Carbon Monoxide Containing Gas
Date: September, 1973
Inventors: David Buben and Clyde Aldridge, Baton Rouge, LA
Assignee: Esso Research and Engineering Company, NJ
Abstract: A process for producing carbon monoxide and hydrogen which comprises contacting a carbon dioxide containing gas with a carbonaceous material in the presence of a cesium salt catalyst in a reaction zone operating at temperatures below 1,600 F.
(Note: The specified "cesium" might sound rare and exotic; but, in point of fact, it is more abundant in the earth's crust than the more familiar tin, tungsten, mercury and silver. And, good ole' Canada, where it is in one place at least commercially produced, has better than two thirds of the world's accessible reserves. It sounds "radioactive", but generally, as found in nature, is not; although radioactive isotopes of it can easily be made in a nuclear reactor. It belongs to the Potassium group of metals, and is used herein because the size of it's atoms enables, as we've been given to understand it, easier transfer of electrons between it and other elements.
Further, although the specified "temperatures below 1,600 F" could still be quite high, that range is still well within the realm of current practical chemical and industrial engineering.)
This invention relates to the production of carbon monoxide and hydrogen.
More particularly it relates to the production of carbon monoxide by a process where carbon dioxide is contacted with carbon in the presence of a catalyst composition in a reaction zone operated at a temperature less than 1,600 F.
In another aspect this invention relates to the production of synthesis gas.
More particularly, the carbon monoxide produced in a first reaction zone by reacting carbon dioxide with carbon in the presence of a catalyst is introduced, along with steam, into a second reaction zone so as to contact a water gas shift reaction catalyst to produce a hydrogen containing gas.
(The above reaction also produces Carbon Dioxide, which is recycled back into the initial reaction to be mixed with additional Carbon Dioxide and reconverted back into Carbon Monoxide, Some of the Carbon Monoxide is then combined with the Hydrogen produced in the "water gas shift reaction" and passed on as final product. It is not a closed Carbon "loop", and a portion of the CO2 does, finally, get "used up". There is, additionally, more to it, which leads to the synergistic production of more Hydrogen, as we attempt to explain in appended comments.)
(A) critical need in today's refinery processes is the need for an economical source of hydrogen. It is known that carbon reacts with carbon dioxide to produce carbon monoxide: C + CO2 = 2CO; and, that carbon monoxide can be treated with steam to produce carbon dioxide: CO + H2O = CO2 + H2.
The hydrogen so produced could be recovered and used in other refinery processes.
The carbon dioxide could be then recycled over a carbon containing material to produce more carbon monoxide.
(We must note, that, should you read the full Disclosure, Esso, predictably, even though they initially specify, as above, only "carbonaceous material", they are careful to describe their process only in terms of how it might apply to conventional petroleum refining, and the reprocessing of highly-carbonaceous oil refining residues, which, as we've described in previous reports, are very much like Coal. And, they mention Coal itself only once, as following.)
According to this invention CO2 is passed through a carbonaceous material such as ... coal char ... or any other solid carbon-containing material ... .
(Thus leaving the door open to botanical, CO2-recycling charcoal, which, in fact, they do mention in an accompanying chart illustrating relative rates of production from both carbonaceous petroleum residuals and charcoal made from coconut husks. And, we see that chart as simply more deliberate obfuscation. There would be no appreciable difference between charcoal made from coconuts and charcoal made from scrub pine trees, which, we attest from personal experience, grow like weeds in the area of Louisiana where the named inventors of our subject process worked, and which could be harvested almost like an annual garden crop.
And, to further emphasize that CO2-recycling and sustainable botanical charcoal can be utilized along with Coal in such a process, we remind you of an earlier report, as accessible via:
More Oklahoma CO2 + Coal = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 4.040,976 - Process of Treating Carbonaceous Material with Carbon Dioxide; 1977; Cities Service Company, OK; A non-catalytic process of reacting solid carbonaceous material with carbon dioxide to produce a carbon monoxide-containing gas, comprising: contacting the carbonaceous material with carbon dioxide (and) wherein ... the material is coal ... (or) is selected from the group consisting of coal, lignite, humates, peat, oil shale, charcoal, coal char, sawdust";
wherein another petroleum company describes very similar technology and specifically states that both Coal and botanical, CO2-recycling charcoal are suitable for such reactions with Carbon Dioxide.)
Claims: A process for the production of a carbon monoxide-containing gas from a carbonaceous material, which comprises: contacting a carbon dioxide-containing gas with a carbonaceous material (at specified rates) in the presence of a catalyst composition comprising a molten mixture of cesium carbonated with lithium carbonate."
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Since Esso suddenly tosses "lithium" into the mix with Cesium, we'll close our excerpts there so that we can summarize and attempt to clarify a few things.
Lithium, in Esso's process, seems to promote the effects of cesium; and, like cesium, there is plenty of lithium to go around, even though it might not be all that well-known. There is, or was, one US Mining company producing it from a clay mineral deposit; and, Canada and South America have plenty of it, with known deposits in Chile, especially, being almost vast. We don't have to deal with OPEC to get it, and, in any case, neither it nor the Cesium is actually consumed, or "used up", to any extent in the process.
The reactive metals cycle through the total Carbon Dioxide recycling and Coal consuming process through a very interesting sequence of reactions that Esso doesn't, perhaps deliberately, fully or clearly explain.
So, here's the deal:
The carbonates of the two metals, and we'll use only Lithium Carbonate, Li2CO3, as the specific example, become "de-carbonated", so to speak, in Esso's specified reaction sequence, as follows:
Li2CO3 + 2C(oal) = 2Li + 3CO (Carbon Monoxide);
as the Carbonate, thus, very productively converts Carbon into Carbon Monoxide.
And, the "free" Lithium then reacts with Water:
2Li + H2O = H2 + Li2O (Lithium Oxide)
To make a little Hydrogen, along with Li2O, which then reacts with Carbon Dioxide:
Li2O + CO2 = Li2CO3;
to reconstitute the Lithium Carbonate, which then goes looking for more hot C(oal).
The total process would actually consume more Carbon - whether Coal or Carbon Dioxide-recycling botanical Charcoal - than it would Carbon Dioxide itself. But, with that ability to use Charcoal in addition to Coal, to react with Carbon Dioxide, the potential for truly meaningful Carbon recycling does exist.
Given the reaction sequences, however, not enough Hydrogen would be co-produced with the Carbon Monoxide to form a genuine synthesis gas, or "syngas", suitable for efficient and complete conversion into hydrocarbons via a Fischer-Tropsch, or similar, process.
So, we could, as seen in:
Consol 1953 Coal to Hydrogen & Methane with No CO2 | Research & Development; concerning: "United States Patent 2,654,661 - Gasification of Carbonaceous Solid Fuels; 1953; Consolidation Coal Company; Abstract: This invention relates to the gasification of carbonaceous solid fuels (wherein a) gaseous product is obtained which contains methane and hydrogen in varying relative proportions depending upon the particular temperature and pressure conditions";
produce additional Hydrogen as the by-product of a Steam gasification process targeted primarily on converting some of our abundant Coal into Methane.
Or, more directly, we could, as seen in:
NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,045,315 - Solar Photolysis of Water; 1977; NASA; Abstract: Hydrogen is produced by the solar photolysis of water";
simply use sunlight to tickle the needed extra Hydrogen out of H2O.
Conversely, we could also, to achieve a proper balance of constituents for hydrocarbon synthesis in the syngas produced by our Carbon-recycling subject process of "United States Patent 3,758,673", simply extract and remove some of the excess product Carbon Monoxide, which we could then, as seen in:
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 production of hydrocarbons"; and, in:
Germany 1957 Carbon Monoxide + H2O = Hydrocarbons | Research & Development; concerning: "United States Patent 2,786,863 - Catalytic Steam-Carbon Monoxide Synthesis; 1957; Abstract: This invention relates to the catalytic steam-carbon monoxide synthesis of hydrocarbons and oxygen-containing compounds";
react one way or the other with nothing but plain old Water to make even more hydrocarbons and alcohols.
In any case, we have herein clear description of a truly immense opportunity to utilize our abundant Coal to help establish an industry, that, consuming only Coal, Carbon Dioxide, renewable Charcoal, and Water, could, in return and for the long foreseeable future, produce for us anything, absolutely anything, we now fight foreign OPEC wars, pollute our oceans, and further enrich Big Oil to keep ourselves supplied with.