Process for the generation of carbon monoxide and hydrogen
First, we promise that we'll actually get to Texaco, but there is some extended preamble to wade through.
Last January, we sent you information concerning two closely-related technologies developed by Pittsburgh's Consolidation Coal Company, wherein both pure Hydrogen and Methane gases could be generated from, as the primary raw materials, Steam and Coal.
That report is accessible on the West Virginia Coal Association's web site via the link:
Consol 1953 Coal to Hydrogen & Methane with No CO2 | Research & Development; and discusses:
"United States Patent 2,654,661 - Gasification of Carbonaceous Solid Fuels; 1953; Consolidation Coal Company, Pittsburgh; The primary object of this invention is to provide an improved two-vessel system for converting carbonaceous solid fuels into ... gas which is rich in methane (and) rich in hydrogen"; and:
"United States Patent 2,654,663 - Gasification of Carbonaceous Solid Fuels; 1953; Consolidation Coal Company, Pittsburgh; The primary object of this invention is to provide an improved two-vessel system for converting carbonaceous solid fuels into gas under substantially thermoneutral conditions (and, which gas) is rich in methane (and) rich in hydrogen (and) substantially free of carbon dioxide".
A close read of the full disclosures of those two patents reveals that the product gases are "substantially free of carbon dioxide" because Consol is utilizing, for the gasification of Coal, an Oxygen donor substance, Strontium Oxide, which, as soon as it donates Oxygen to the Carbon, is available to react with any Carbon Dioxide floating around, and thereby form Strontium Carbonate, which can then be easily recovered and heated to reconvert it into the catalytic and reactive Strontium Oxide, in a separate procedure that itself generates a nearly-pure stream of Carbon Dioxide, which can be easily captured and collected.
The discharged CO2, then, in Consol's view, can be reacted with Calcium Oxide, and be converted into Calcium Carbonate, i.e., limestone, which can then be safely disposed of anywhere; though, as we have once or twice documented in other reports, such particulate Calcium Carbonate does have some industrial manufacturing uses, often as an inert filler and extender for various plastics.
In another report, documenting the later development of similar, though more advanced, technology:
Oklahoma Oxygen Donor Coal Gasification | Research & Development; concerning the: "United States Patent 4,070,160 - Gasification Process with Zinc Condensation on the Carbon Source; 1978; Phillips Petroleum Company: Abstract: In a process for gasifying solid carbon sources such as coal utilizing zinc oxide as the oxygen donor";
we saw that an Oxygen donor, Zinc Oxide, could be used, which, after recovery as elemental Zinc from the Coal gasification process, could generate Hydrogen for combination, and subsequent catalytic processing into hydrocarbons, with the nearly-CO2-free Carbon Monoxide generated from Coal via that Oxygen donor process.
Other technologies do utilize Calcium Oxide as a Carbon Dioxide absorbent, in a reaction which forms Calcium Carbonate, as in the above-noted Consol process of preparing CO2 for disposal once the CO2 was efficiently captured by the more-easily recyclable Strontium Oxide.
Such a CO2-absorption process is clearly defined in a very recent US Patent disclosing technology designed to help out one of the most prolific industrial emitters of Carbon Dioxide: the cement industry.
And, it's somewhat surprising to see who developed that technology, in links to and excerpts from:
"United States Patent: 7976628 - Carbon Dioxide Capture from a Cement Manufacturing Process
Date: July, 2011
Inventors: Gerald Blount, et. al., South Carolina
Assignees: Savannah River Nuclear Solutions, LLC, and Clemson University, SC
This invention was made with Government support under Contract No. DE-AC09-08SR22470 awarded by the United States Department of Energy. The Government has certain rights in the invention.
(Note: In what we have previously explained is, from our point of view, an, at best, unsavory situation, our United States Department of Energy, in it's wisdom, has started farming out management of our critical United States National Laboratories to consortiums of private companies and public entities. Those consortiums, although paid in the first place to manage the Labs, are then entitled to share ownership of any inventions developed in those National Labs, whose operations are funded with, and whose scientists are paid with, the taxes collected from each and every US citizen. For more on who now actually owns this invention that all of us bought and paid for go to:
Savannah River Nuclear Solutions, LLC; where you will discover that both Fluor Corporation and Honeywell are among the beneficiaries of our unwitting, and thus compulsory, largesse.)
Abstract: A process of manufacturing cement clinker is provided in which a clean supply of CO2 gas may be captured. The process also involves using an open loop conversion of CaO/MgO from a calciner to capture CO2 from combustion flue gases thereby forming CaCO3/CaMg(CO3)2. The CaCO3/CaMg(CO3)2 is then returned to the calciner where CO2 gas is evolved. The evolved CO2 gas, along with other evolved CO2 gases from the calciner are removed from the calciner. The reactants (CaO/MgO) are feed to a high temperature calciner for control of the clinker production composition."
What the above means is that they are using common limestone, which is most often in nature found as an intimate blend of Calcium Carbonate and Magnesium Carbonate (CaCO3 and MgCO3) in various proportions, to create Carbon Dioxide absorbents, Calcium Oxide, CaO, and Magnesium Oxide, MgO, by simply heating the Carbonates, which drives off nearly-pure Carbon Dioxide.
The two Oxides are then free to be recycled and to capture more CO2, or, as in the USDOE-Clemson process, simply sent on for the production of cement.
The point is, that, if we want to, we can, as Consolidation Coal told us back in 1953, capture Carbon Dioxide pretty efficiently with some pretty common stuff, and, as our USDOE's proxies just recently told us, as immediately above, we can rather easily recover nearly pure CO2 from that pretty common stuff once the CO2 has been extracted from flue gases.
And, keep in mind that Consol was doing it, back in 1953, in the course of making blends of Methane and Hydrogen, pretty efficiently, out of Coal.
Okay, then.
Once we have the pure CO2, as could be so easily extracted and produced from a stream of Methane and Hydrogen made, back in 1953, by Consol, from Coal, following, as excerpted from the initial link far above in this dispatch, is what good ole' Texaco, since absorbed into the Chevron conglomerate, told us we could do with that Methane, and that CO2, but, with an encouraging "twist" we try to explain, again all the way back in 1953:
"United States Patent 2,660,521 - Process for the Generation of Carbon Monoxide and Hydrogen
Date: November, 1953
Inventor: Charles Teichmann, NY
Assignee: Texaco Development Corporation, NYC
(Perhaps of interest, the first page of the full document is actually a schematic illustration of the process, showing where different raw materials are added to it. The very first raw material ingredient named, at the very top of the illustration, on that very first page, is Carbon Dioxide.)
Abstract: This invention relates to a process for the preparation of carbon monoxide and hydrogen by the partial combustion of a carbonaceous fluid fuel.
(Don't be distracted. A "fluid" can be either a liquid or a gas.)
In one of its more specific aspects, the invention comprises subjecting a gaseous hydrocarbon to partial combustion to form carbon monoxide and hydrogen free from residual methane and free carbon.
(Such "free carbon", we remind you, as we've documented in many previous reports, is composed of fine particles of carbon, a soot, that results when Methane and Carbon Dioxide are reformed alone, in a process labeled "bi-reforming".
"Tri-reforming", on the other hand, as we've reported, for just one out of now many examples, in
More Penn State CO2 Recycling with Methane | Research & Development | News; concerning, among other things, the report: "Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios; Pennsylvania State University; The ... tri-reforming process is a synergetic combination of CO2 reforming, steam reforming, and partial oxidation of methane in a single reactor for effective production of industrially useful synthesis gas (syngas)";
utilizes Steam, H2O, in addition to Methane and Carbon Dioxide, both to improve the H2-CO ratio of the resultant hydrocarbon syngas and to prevent the deposition of, and to more fully utilize, Carbon.)
In accordance with my invention, carbon monoxide and hydrogen are prepared by controlled oxidation of the fuel with an oxygen-rich gas in a combustion gas turbine.
The gases are generated (with a) heat content ... which is at a high level due to the exothermic nature of the oxidation reaction (and, that heat) is partially converted to mechanical energy by means of a gas turbine in which the gases are subjected to expansion and cooling.
The carbon monoxide and hydrogen are produced in the combustion section of the turbine and immediately subjected to cooling and pressure reduction by expansion in the blading of the turbine.
The power thereby generated may be used advantageously in compressing reactant gases used in the process, e.g., in supplying power to an Oxygen plant."
(We're compelled to interrupt to offer some explanation. This Texaco "tri-reforming" process is driven by heat energy, and, the actual reforming reaction is designed to be more of a partial combustion process, where the Methane is partially oxidized, with the Steam and Carbon Dioxide, in combination with some added Oxygen to supply exothermic oxidation reactions, which reactions provide heat for the endothermic "reforming" reactions between the CO2, Steam and remaining Methane.
As in other, similar technologies about which we've reported, there is an excess of heat energy which can be produced, almost as a by-product, and utilized for other constructive purposes
There is sufficient heat energy, in fact, to drive a turbine and generate power for other needed processes, which Texaco, in this case, suggests to be one which produces the necessary purified Oxygen.
The amount of Oxygen utilized is controlled, so that the oxidation of the Methane is only partial, and thus results in formation of only more Carbon Monoxide, and H2O, as opposed to CO2.
Such a process, which requires the addition of purified Oxygen, at some, even though limited, additional expense, is contrasted with later processes, such as the one cited above, from Penn State University, wherein catalysts have been found which limit the need for such partial oxidation of the Methane to provide heat energy.
Further, in addition to improved catalysis, environmental energy can then be harnessed to provide the thus catalytically-reduced heat requirements of the CO2-CH4-H2O reaction , as indicated in:
USDOE 1990 Solar CO2-Methane Recycling-Reforming | Research & Development; concerning: "Solar Reforming of Methane; 1990; Sandia National Labs, NM (USDOE); Solar reforming of methane (CH4) with carbon dioxide (CO2) was achieved".
Even further, it is feasible to use Solar energy to, in the first place, make the needed Methane out of Carbon Dioxide itself, as we documented in our report, of what could be seen as a space-age advance on the 1912 Sabatier process, again from Penn State University, in:
Penn State Solar CO2 + H2O = Methane | Research & Development; concerning: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; The Pennsylvania State University; 2009; Efficient solar conversion of carbon dioxide and water vapor to methane".)
The present invention may be used for the generation of synthesis gas feed for the production of carbon monoxide and hydrogen in the (product) gases.
(And,) it is possible ... to vary the molecular ratio of carbon monoxide and hydrogen by varying the quantity of carbon dioxide supplied.
(That is a valuable attribute, since) different catalysts used for the catalytic conversion of carbon monoxide and hydrogen into hydrocarbons, oxygenated hydrocarbons (i.e., alcohols), etc., are most effective with different molecular ratios of carbon monoxide to hydrogen (and) it is most important to be able to vary the ratio of carbon monoxide to hydrogen in the synthesis gas.
Carbon Dioxide, formed in the catalytic conversion of carbon monoxide and hydrogen into the desired products may be recycled to the (initial gas reforming) turbine.
(As we've previously documented, some, especially older, versions of catalyzed synthesis reactions between Carbon Monoxide and Hydrogen, to form hydrocarbons, can result in the co-production, from the synthesis reaction, of some, relatively minor, amounts of CO2, which can, perhaps obviously, be collected and recycled back into the reforming reaction and be added to the initial mix of reactant gases.)
Carbon Dioxide reacts endothermically with the hydrocarbon to yield carbon monoxide and hydrogen.
Alternatively, the carbon dioxide may be admixed with the product gases from the combustion section of the turbine ...
(Knew a lot about alternatives for recycling CO2 more than half a century ago, didn't we?)
(Another) function served by the carbon dioxide is that it affords a means of varying the ratio of carbon monoxide to hydrogen in the product gases (and, it is possible) to vary the molecular ratio of the carbon monoxide and hydrogen by varying the quantity of carbon dioxide supplied.
(Furthermore,) steam, prepared, for example, by heat exchange with the exhaust gas ... may be supplied (to) serve the same dual function as carbon dioxide ... .
It would serve as a diluent and since steam also reacts endothermically with ... methane ... by (adding) varying quantities of steam ... it is possible to alter the molecular ratio of the ... carbon monoxide and hydrogen in the (product) gases.
(Again, that is a valuable attribute, since) different catalysts used for the catalytic conversion of carbon monoxide and hydrogen into hydrocarbons, oxygenated hydrocarbons (i.e., alcohols), etc., are most effective with different molecular ratios of carbon monoxide to hydrogen (and) it is most important to be able to vary the ratio of carbon monoxide to hydrogen in the synthesis gas."
------------------
And, we can "vary the ratio of carbon monoxide to hydrogen in the synthesis gas", to make it suitable for the production, either, of pure "hydrocarbons", or, of alcohols, by adding more, or less, Carbon Dioxide, recovered, perhaps, from the fermentation vats of a clean, green Corn Ethanol production facility, to an initial blend of Steam and Methane.
Now, we can make that Carbon Dioxide-recycling Methane, as we noted in our citation of: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; The Pennsylvania State University", using environmental energy, out of Carbon Dioxide itself.
Or, we could, as in the Consol processes we cited above, of US Patents "2,654,661" and "2,654,663", both for the "Gasification of Carbonaceous Solid Fuels", just make it from Coal, along with some useful amounts of Hydrogen.
Which extra Hydrogen, by the way, could be employed in a more basic Sabatier reactor, as in:
NASA Rocket Fuel from CO2 | Research & Development; which informs that: "Although Mars is not rich in methane, methane can be manufactured there via the Sabatier process: Mix some carbon dioxide (CO2) with hydrogen (H), then heat the mixture to produce CH4 and H20 -- methane and water";
to convert more Carbon Dioxide into more Methane, which could be added to the process of our subject process of Texaco's "United States Patent 2,660,521" to help convert even more Carbon Dioxide into hydrocarbon synthesis gas.
We acknowledge that the Consol processes also generate some CO2, but, a close read reveals that they makes that by-product CO2 only in relatively small amounts.
There should be enough Methane resulting from the Consol process to consume, through the process of our subject, Texaco's "United States Patent 2,660,521", both all of the CO2 co-produced with the Methane and Hydrogen, from Coal, in the production of a "synthesis gas" suitable, as Texaco specifies, for "conversion ...into hydrocarbons (and) oxygenated hydrocarbons", and, some additional amount of CO2 recovered from outside any of these Carbon Conversion processes themselves, such as, perhaps, from the vent gases arising from an all-natural geothermal energy well tapping into the CO2-laden hot water available in some locations.
But, no matter where we get the Methane, we can then, as affirmed herein by Texaco and our own United States Government well more than half a century ago, react it with Water and Carbon Dioxide, perhaps, as in our above citation of "United States Patent 7,976,628 - Carbon Dioxide Capture from a Cement Manufacturing Process", recovered from an industrial operation that fortuitously makes very generous quantities of it, as the valuable by-product of an otherwise important manufacturing process, and produce, through such reaction, according to Texaco, a blend of "carbon monoxide and hydrogen", a "synthesis gas", which can then be converted, via long-known catalytic processes into "hydrocarbons" and "oxygenated hydrocarbons".