Continuous process for effecting catalytic reactions

Most of us who grew up in West Virginia, and other Coal-mining states, in the 1950's and 1960's, at one time or another became acquainted with the old, traditional Coal miner's "cap lamp": an ingenious little affair that trickled Water into a closed reservoir of Calcium Carbide, thereby generating Acetylene gas that was directed through a nozzle in the center of a polished metal reflector, where it was ignited with a flint spark wheel similar to that on the old Zippo lighter you used to fire up the L&M's you pilfered from your Dad.

 

 

Similar technology was, as well, at one time used in industrial applications to generate, on-site, the Acetylene needed to fuel welding and cutting torches.

The Calcium Carbide was made, basically, by reacting, or roasting, Limestone blended with red-hot Coal.

In essence, though not, strictly speaking, an entirely accurate way of putting it, the Calcium served as a sort of catalyst that conveyed Carbon from Coal into reactions with Water, to form hydrocarbons; and, which reactions the Calcium also promoted.

As it happens, metals other than Calcium can be converted into Carbides; they can be so converted through processes other than roasting them with Coal; and, the resulting Carbides can then be reacted in such a way so as to yield a variety of hydrocarbon products other than, and in addition to, Acetylene.

Comment, with some additional links and excerpts concerning the implications of it all, follows excerpts from the initial link to:

"United States Patent 2,409,235 - Process for Effecting Catalytic Reactions

Date: October, 1946

Inventor: Harold Atwell, NY

Assignee: The Texas Company (aka: Texaco), New York City

Abstract: This invention relates to a continuous process for effecting catalytic reactions, and more particularly for effecting catalytic conversion of gaseous reactants by the action of a solid catalyst in finely divided or powdered form for the production of normally liquid carbonaceous compounds.

The invention contemplates forming normally liquid compounds from carbon and hydrogen by the action of a solid hydrogenating catalyst containing a carbide forming metal, such as, cobalt, iron or nickel.

More specifically, the invention contemplates a two-stage continuous process, in the first stage of which the catalyst is subjected to contact with a volatile carbon compound under conditions adapted to form metallic carbide, and in the second stage of which the catalyst containing metallic carbide is separately subjected to contact with hydrogen under conditions adapted to produce normally liquid carbonaceous compounds, such as hydrocarbons.

In accordance with the invention, a volatile carbon compound, such as carbon monoxide is subjected to contact with a solid catalyst containing cobalt, iron or nickel at a temperature in the range (of) 350 to 425F, whereby formation of the carbide of cobalt occurs to a substantial extent in accordance with the following chemical equation: 2Co(balt) + 2CO = Co2C + CO2.

The catalyst containing the carbide of cobalt or other metal is then passes to a separate treating zone where it is treated with hydrogen at a somewhat lower temperature in the range (of) 200 to 400F and under conditions such that the carbide undergoes decomposition, the liberated carbon reacting with hydrogen to form hydrocarbon products mainly heavier than methane.

(Methane wouldn't be a bad thing to have, mind you, since, as seen for just one instance in:

More Standard Oil 1944 CO2 + CH4 = Hydrocarbons | Research & Development; concerning: "United States Patent 2.347.682 - Hydrocarbon Synthesis; 1944; Assignee: Standard Oil Company of Indiana; Abstract: This invention relates to an improved method and means for effecting the synthesis of hydrocarbons from carbon monoxide and hydrogen (wherein a) methane-carbon dioxide-steam mixture into a gas consisting chiefly of hydrogen and carbon monoxide (suitable for catalytic conversion) into high quality motor fuels";

we can react Methane with Carbon Dioxide and thereby synthesize liquid "motor fuels".)

Carbon dioxide produced in the primary stage ... may be reduced to carbon monoxide by contact with carbon or may be reacted with methane to produce carbon monoxide and hydrogen ... .

(Just as in the process above of "United States Patent 2.347.682"; or, as Texaco themselves explain, in:

Texaco CO2 + Coal = Hydrocarbon Synthesis Gas | Research & Development; concerning: "United States Patent 3,976,442 - Synthesis Gas from Gaseous CO2-Solid Carbonaceous Fuel Feeds; 1976; Assignee: Texaco, Incorporated; Abstract: This is an improved continuous partial oxidation process for producing synthesis gas or fuel gas from gaseous CO2 (and) solid carbonaceous fuel feeds";

wherein it is again confirmed that Carbon Dioxide can be reacted with hot Coal, with the conversion of them both into Carbon Monoxide.)

The carbon monoxide so obtained is thus available for recycling to the primary reaction stage.

Likewise, hydrogen obtained by reacting methane with carbon dioxide is available for recycling to the secondary stage of the process.

The methane used for reaction with carbon dioxide advantageously includes that obtained by separation from the hydrocarbon products of the process.

(In other words, Methane is produced in some reduced quantities as an unwanted by-product of this process; but, it can be reacted with another unwanted by-product of the process, Carbon Dioxide, with both of them being converted thereby into more of the desired Hydrogen-Carbon Monoxide synthesis gas.)

Additional methane may be obtained from an outside source.

(And, we suggest as an appropriate "outside source" of Methane, that described in our earlier report:

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".)

A further feature involves synthesizing hydrocarbons without the formation of water (which feature) greatly reduces the complexity and energy requirements.

(An even) further feature involves utilizing carbon dioxide ... .

Claims: A continuous process for catalytically forming normally liquid hydrocarbons from carbon and hydrogen by the use of a solid hydrogenating catalyst containing a carbide-forming metal ... ."

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There are a number of perspectives from which to view the process of our subject invention.

In the, perhaps, most direct aspect, it is a "condensed" form of the Fischer-Tropsch reaction, whereby Carbon Monoxide and Hydrogen are catalyzed together and made to form hydrocarbons.

In this case, however, and perhaps most advantageously, Carbon Monoxide itself is not directly involved in the Hydrocarbon synthesis reaction with the Hydrogen. Carbon extracted from Carbon Monoxide is carried into the reaction with Hydrogen by the metal catalyst; and, the result is a higher concentration of more energy-dense true hydrocarbons being produced, as opposed to the otherwise concurrent production of "oxygenated" hydrocarbons, i.e., alcohols, along with the more-desired hydrocarbon petroleum substitutes.

Oxygen, in other words, is excluded by this process from the Hydrocarbon synthesis reactions.

Free Hydrogen is required for reaction with the metal carbide, to form the Hydrocarbons; and, although Texaco posits that at least some of it can be gotten from co-produced Methane recycled back into the process, that is simply a Hydrogen-conserving measure, and another source of supply is needed.

For that purpose, we suggest an option similar to that we recently reported in:

Hydrogen from Wind Power | Research & Development; concerning: "United States Patent 7,329,099 - Wind Turbine and Energy Distribution System; 2008";

which describes how Wind can be used to generate electricity, with the electricity being directly used to "split" Water, H2O, into Oxygen and Hydrogen.

Other, similar opportunities for the use of various environmental, or environmentally-derived and renewable, energies to generate the needed Hydrogen exist, as well, as we have previously documented and as we will further report.

And, to provide the Carbon Monoxide with which the Carbon-carrying catalyst of our subject "United States Patent 2,409,235 - Process for Effecting Catalytic Reactions", as in, above, "carbon monoxide is subjected to contact with a solid catalyst containing cobalt, iron or nickel", is formed, we remind you again, that, as seen, for just another example, in our earlier report of:

1915 CO2 Recycling | Research & Development | News; which concerns, in part: "United States Patent 1,163,922 - Producing Carbon Monoxid from Carbon Dioxid; 1915; This invention relates to the production of carbon monoxid (CO) gas and the controlling method embraces mixing powdered carbon and carbon dioxid (CO2) gas under sufficiently high temperature to cause a carbon molecule to combine with one of the oxygen elements of the CO2, resulting in 2CO";

we can make that Carbon Monoxide required by the process of USP 2,409,235, to make the metal carbide catalysts, needed for the synthesis of "normally liquid carbonaceous compounds, such as hydrocarbons", by reacting Carbon Dioxide, recovered from whatever handy and convenient source, with red-hot Coal.


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