United States Patent Application: 0120245236
As we've recently been documenting, in, for just two examples:
West Virginia Coal Association | Connecticu?t and Honda 2012 CO2 and H2O to Hydrocarbo?n Fuels | Research & Development; concerning: "United States Patent Application 20120241327 - Materials and Design for an Electrocatalytic Device and Method which Produces Carbon Nanotubes and Hydrocarbon Transportation Fuels; September 27, 2012; Inventors: Steven Suib, et. al.; Assignee: The University of Connecticut and Honda Motor Company; The present teachings are directed toward an electrocatalytic cell" by use of which "liquid hydrocarbon fuels can be generated directly from feedstocks containing only carbon dioxide and water"; and:
West Virginia Coal Association | Connecticut Recycles CO2 into Hydrocarbons | Research & Development; concerning, in part: "United States Patent 7,964,084 - Methods and Apparatus for the Synthesis of Useful Compounds; June 21, 2011; Inventors: Victor Stancovski, Steven Suib, et. al.;Assignees: Catelectric Corporation and the University of Connecticut; Abstract: The present invention relates to methods and apparatus for activation of a low reactivity compound (and) comprises introducing the low reactivity chemical compound to a catalyst (with) an oxidizing (or) reducing agent (to produce) a useful product ... wherein the low reactivity compound comprises CO2 (and) the useful product comprises at least one of an alcohol";
the University of Connecticut has been at work with corporate partners on the development of technologies which would enable us to begin efficiently converting the environmental lobby's Coal-beating club, Carbon Dioxide, into OPEC's USA-beating club, liquid hydrocarbon fuels.
We can, in other words, save both King Coal and Uncle Sam from the beatings, if we could all just learn to close our mouths during this election season and pay a little unbiased attention to the apolitical college lessons being provided to us.
Since we understand that everyone's anxious to get out and vent their emotions today with the stroke of a pen, the push of a button or the de-hanging of a chad, we'll try to keep our dissertation herein relatively brief.
In a United States Patent Application published right alongside the above-cited "United States Patent Application 20120241327 - Materials and Design for an Electrocatalytic Device and Method which Produces Carbon Nanotubes and Hydrocarbon Transportation Fuels", a patent application that, in fact, cites "United States Patent Application 20120241327", the same team of University of Connecticut inventors discloses an essential component of that "Device and Method" for generating "liquid hydrocarbon fuels ... directly from ... carbon dioxide and water": the catalyst for the "electrocatalytic cell".
As seen in excerpts from the initial link in this dispatch to:
"United States Patent Application 20120245236 - Fischer-Tropsch Catalysts Containing Iron or Cobalt Selective Towards Higher Hydrocarbons
FISCHER-TROPSCH CATALYSTS CONTAINING IRON OR COBALT SELECTIVE TOWARDS HIGHER HYDROCARBONS - Suib, Steven L.
Date: September 27, 2012
Inventors: Steven Suib, et. al., CT and OH
(Presumed Assignee, not yet officially published: the University of
Connecticut)
Abstract: Cryptomelane-type manganese oxide octahedral molecular sieves (OMS-2) supported Iron and Cobalt catalysts are utilized in a method for producing hydrocarbons by a Fischer-Tropsch mechanism. The hydrocarbon producing method includes providing a catalyst of a manganese oxide-based octahedral molecular sieve nanofibers with an active catalyst component of at least one of iron, cobalt, nickel, copper, manganese, vanadium, zinc, and mixtures thereof, and further containing an alkali metal. The formation of iron carbides and cobalt carbides by exposing the catalyst to conditions sufficient to form those carbides is also taught. After the catalyst has been appropriately treated, a carbon source and a hydrogen source are provided and contacted with the catalyst to thereby form a hydrocarbon containing product. The catalyst have high catalytic activity and selectivity (75%) for C2+ hydrocarbons in both CO hydrogenation and CO2 hydrogenation. Highly selective syntheses of high value jet fuel, C2-C6 alkenes, C2-C6 carboxylic acids; .alpha.-hydroxylic acids and their derivatives have been realized by tuning the oxidation ability of OMS-2 supports and by doping with Copper ions.
(First, the dreadfully complicated-sounding "Cryptomelane-type manganese oxide octahedral molecular sieves (OMS-2)", is actually, as can be learned via:
Cryptomelane - Wikipedia, the free encyclopedia; a fairly common and innocuous type of manganese mineral widely found in nature.
Second, in addition to "jet fuel", the "C2-C6 alkenes" produced herein from Carbon Dioxide, as taught by:
Alkene - Wikipedia, the free encyclopedia; could "serve as a feedstock for the petrochemical industry because they can participate in a wide variety of reactions".
Third, the "OMS-2" is just shorthand for, as seen in:
ingentaconnect Manganese Dioxide as a New Cathode Catalyst in Microbial Fuel Cel...; "This study focused on manganese oxides with a cryptomelane-type octahedral molecular sieve (OMS-2) structure to replace platinum as a cathode catalyst in microbial fuel cells";
a type of catalyst, or, perhaps more accurately, a type of catalyst structure, that is, in certain informed circles dealing with such matters, familiar and understood.)
Claims: A catalyst comprising manganese oxide-based octahedral molecular sieves, at least one of iron, cobalt, nickel, copper, manganese, vanadium, zinc, and mixtures thereof, and an alkali metal.
(And) wherein iron comprises Fe3C (Iron Carbide, and) wherein cobalt comprises ... Co3C.
(And) wherein the alkali metal comprises potassium ... (in an amount specied).
The catalyst ... wherein when a mixture of cobalt and copper is present (in a specified ratio).
The catalyst ... wherein the alkali metal comprises potassium present as potassium hydrogen carbonate.
A method for producing hydrocarbons comprising providing a catalyst comprising a manganese oxide-based octahedral molecular sieve, at least one of iron, cobalt, nickel, copper, manganese, vanadium, zinc, and mixtures thereof, and an alkali metal; exposing the catalyst to conditions sufficient to form carbides of either iron or cobalt; providing a carbon source and a hydrogen source; contacting the carbon source and the hydrogen source with the catalyst, and producing a hydrocarbon.
The method ... wherein the carbon source comprises at least one ... of carbon monoxide and carbon dioxide.
(Either "carbon monoxide" or "carbon dioxide" will do, in other words. We can use CO2 extracted right out of the air or any other source.)
The method ... wherein the hydrogen source comprises at least one member selected from the group consisting of hydrogen and water.
(Either elemental "hydrogen" or "water" can serve as the Hydrogen source, although the choice will influence the product distribution resulting from the CO2 hydrogenation.)
The method ... wherein exposing comprises heating the catalyst to a temperature of at least 280 C under an atmosphere comprising hydrogen and ... carbon dioxide.
The method ... wherein the atmosphere ranges in pressure from about 2 atmospheres to about 20 atmospheres.
(The process is fairly hot, "280 C", and could require, "20 atmospheres", some pretty high pressure.)
The method ... wherein exposing comprises heating the catalyst to a temperature of at least about 320 C. and no greater than about 450 C under an atmosphere comprising hydrogen and ... carbon dioxide.
(We have edited our excerpts to emphasize the potential for direct utilization of CO2. Carbon Monoxide is specified as frequently as Carbon Dioxide, which would result in a slightly different mix of product hydrocarbons. If Carbon Monoxide and the hydrocarbons which result from it's use are preferable, or desired as well, then, as seen, for only one example, in our report of:
West Virginia Coal Association | Germany 98% Pure Carbon Monoxide from Coal, CO2 and O2 | Research & Development; concerning: "Carbon Monoxide from Coke, Carbon Dioxide and Oxygen;1986; Lurgi GmbH, Frankfurt (Germany); Abstract: Many valuable organic chemicals-both as intermediate or final products-can be made from high purity carbon monoxide (and) merely two process steps are required to convert coke to high purity CO. The purpose of the first process step is to gasify coke using a mixture of CO2 and O2 as gasification agent while the second one serves to remove sulfur compounds and residual CO2. Both processes are commercially proven. Depending on the quality of the feedstocks the produced gas shows a CO concentration of 97 to 98.5% by volume. This CO level makes for an excellent feedstock for most syntheses";
we can make some pretty pure Carbon Monoxide from Carbon Dioxide and some "coke", perhaps made from a little of our abundant Coal.)
Background and Field: The present teachings are directed towards a method for producing hydrocarbons by a Fischer-Tropsch mechanism and the catalysts for the method. The hydrocarbon producing method includes providing a catalyst of a manganese oxide-based octahedral molecular sieve nanofibers with at least one of iron, cobalt, nickel, copper, manganese, vanadium, zinc, and mixtures thereof, and further containing an alkali metal. The formation of iron carbides and cobalt carbides by exposing the catalyst to conditions sufficient to form those carbides is also taught. After the catalyst has been appropriately treated, a carbon source and a hydrogen source are provided and contacted with the catalyst to thereby form a hydrocarbon containing product. The characteristics of the hydrocarbon products can be controlled by the formulation and treatment of the catalyst.
Summary: The present disclosure teaches a catalyst based on manganese oxide-based octahedral molecular sieve nanofibers, (also known as synthetic cryptomelane), an active catalyst metal of at least one of iron, cobalt, nickel, copper, manganese, vanadium, zinc, and mixtures thereof, and an alkali metal typically present as a promoter. In some embodiments of the catalyst, the active catalyst metals are present as phases of iron carbide or cobalt carbide.
A method for producing hydrocarbons by an FT mechanism from CO and/or CO2 hydrogenation is also disclosed herein. This method can include providing a catalyst composed of a manganese oxide-based octahedral molecular sieve nanofiber, at least one of iron, cobalt, nickel, copper, manganese, vanadium, zinc, and mixtures thereof, and an alkali metal. The method also features the formation of iron carbides and cobalt carbides by exposing the catalyst to conditions sufficient to form those carbides. After the catalyst has been appropriately treated, a carbon source and a hydrogen source are provided and contacted with the catalyst to thereby form the desired hydrocarbon containing product.
The presently disclosed OMS-2 supported Co and Fe catalysts can be utilized for the highly selective and efficient production of jet fuel, alkenes, ... and their derivatives via CO2 ... hydrogenation".
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As in other Carbon Dioxide consumption and utilization technologies we've reported to you, such as that seen in:
West Virginia Coal Association | US Navy Improves CO2 Hydrogenation Catalyst | Research & Development; concerning: "United States Patent Application 20110105630 - Catalytic Support for use in Carbon Dioxide Hydrogenation; 2011; Assignee: The Government of the USA as represented by the Secretary of the Navy; Abstract: A catalyst support which may be used to support various catalysts for use in reactions for hydrogenation of carbon dioxide ... . A method for hydrogenation of carbon dioxide comprising the step of reacting hydrogen and carbon dioxide (wherein) CO2 and H2 can ... be reacted over a heterogeneous catalyst to form hydrocarbons of desired chain length and type";
the availability of molecular, elemental Hydrogen does allow some latitude in selecting the types of hydrocarbons and other products, as in "hydrocarbons of desired chain length and type", which can be produced through the hydrogenation of Carbon Dioxide.
And, we remind you, that, as seen for only one example in:
West Virginia Coal Association | Chicago Hydrogen from H2O | Research & Development; concerning: "United States Patent 4,793,910 - Photoelectrochemical Cell for Unassisted Photocatalysis; 1988; Assignee: Gas Research Institute, Chicago; Abstract: A multielectrode photoelectrochemical cell ... which ... contains two bipolar electrode panels for photoelectrochemical reactions such as water photolysis to produce H2 (and) O2";
a number of efficient processes exist which enable the use of freely-available environmental energy, in the above case sunlight, to generate, if desired, elemental Hydrogen from nothing but plain old Water.
In sum, the catalyst disclosed and the process described by our subject herein, "United States Patent Application 20120245236 - Fischer-Tropsch Catalysts Containing Iron or Cobalt Selective Towards Higher Hydrocarbons"; is just further confirmation of the Truth we have now many times documented for you:
Carbon Dioxide, as it arises in only a small way, relative to natural and inescapable sources of emission, such as the inexorable processes of planetary volcanism, from our essential use of Coal in the generation of abundant and truly economical electric power, is a valuable raw material resource. We can reclaim Carbon Dioxide, from whatever convenient source, and, as explained herein by scientists at the University of Connecticut, then convert that Carbon Dioxide efficiently into, among other things, "jet fuel".
