United States Patent: 8987160

Carbon Dioxide, as we might conveniently and profitably harvest from the exhaust gases co-produced by our economically essential use of Coal in the generation of truly abundant and genuinely affordable electric power, is a valuable raw material resource.

We can harvest Carbon Dioxide from whatever source most convenient to us, and then use and consume that Carbon Dioxide as the key raw material in processes that synthesize, as end products, hydrocarbon chemicals and fuels.

 

We've previously documented the interests and achievements of both the University of Connecticut and Japan's Honda Motor Company in the development of technologies wherein Carbon Dioxide, again as we might harvest as a byproduct from our use of Coal in the generation of reliable electric power, is used and consumed as the key raw material in such processes which synthesize hydrocarbon fuels.

As seen, for instance, in our reports of:

Honda USA 2014 Solar CO2 to Methane | Research & Development | News; concerning: "United States Patent 8,840,772 - Solar Fuel Cell; 2014; Inventor: Ting He, Dublin, Ohio; Assignee: Honda Motor Company, Ltd., Tokyo, Japan; Abstract: The present teachings are directed to a method of converting water and a carbon-containing compound, such as CO2, into a hydrocarbon through a process of absorbing sunlight on a light-absorbing component to photoelectrochemically oxidize water and reacting the products from that water oxidation reaction over a catalyst with the carbon-containing compound to produce the desired hydrocarbon compound"; and:

 Connecticut Recycles CO2 into Hydrocarbons | Research & Development | News; concerning, in part:

"United States Patent 7,964,084 - Methods and Apparatus for the Synthesis of Useful Compounds; 2011; Inventors: Victor Stancovski, Steven Suib, et. al., CT;Assignees: Catelectric Corporation and the University of Connecticut, CT; Abstract: The present invention relates to methods and apparatus for activation of a low reactivity, non-polar chemical compound. In one example embodiment, the method comprises introducing the low reactivity chemical compound to a catalyst. At least one of (a) an oxidizing agent or a reducing agent and (b) a polar compound is provided to the catalyst and the chemical compound. An alternating current is applied to the catalyst to produce an activation reaction in the chemical compound. This activation reaction produces a useful product. ... (The) method ... wherein: the low reactivity chemical compound comprises CO2; and the useful product comprises at least one of an aldehyde, trioxane, ethane, ethylene, formaldehyde, and paraformaldehyde";

they both have been at work, separately, and, as seen in:

Connecticu?t and Honda 2012 CO2 and H2O to Hydrocarbo?n Fuels | Research & Development | News; concerning:  "United States Patent Application 20120241327 - Materials and Design for an Electrocatalytic Device and Method which Produces Carbon Nanotubes and Hydrocarbon Transportation Fuels; 2012; Inventors: Steven Suib, et. al.; Assignee: The University of Connecticut and Honda Motor Company, Tokyo"; wherein it's said, that: "liquid hydrocarbon fuels can be generated directly from feedstocks containing only carbon dioxide and water";

together, developing technologies wherein Carbon Dioxide can be productively utilized in the synthesis of both substitute natural gas Methane and "liquid hydrocarbon fuels".

Another of our reports concerning the University of Connecticut's Carbon Dioxide recycling developments is accessible via:

Connecticut Formulates CO2 Recycling Catalyst | Research & Development | News; and concerned: "United States Patent Application 20120245236 - Fischer-Tropsch Catalysts Containing Iron or Cobalt Selective Towards Higher Hydrocarbons; 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".

As it happens, our United States Government, less than two weeks ago, confirmed the validity and the practicability of the above "United States Patent Application 20120245236", and, in so doing revealed that the University of Connecticut's partner in the development of that CO2-to-hydrocarbon technology was, as in the above-cited "US Patent Application 20120241327 - Materials and Design for an Electrocatalytic Device and Method which Produces Carbon Nanotubes and Hydrocarbon Transportation Fuels", again Japan's Honda Motor Company.

As seen in excerpts from the initial link in this dispatch to the recent:

"United States Patent 8,987,160 - Fischer-Tropsch Catalysts Containing Iron or Cobalt Selective Towards Higher Hydrocarbons

Fischer-tropsch catalysts containing iron or cobalt selective towards higher hydrocarbons - Honda Motor Co., Ltd.

Date: March 24, 2015

Inventors: Steven Suib, et. al, CT and OH

Assignees: Honda Motor Company, Ltd., Tokyo, and The University of Connecticut

Abstract: Cryptomelane-type manganese oxide octahedral molecular sieves (OMS-2) supported Fe (Iron) and Co (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 (has) been realized by tuning the oxidation ability of OMS-2 supports and by doping with Cu2+ (copper) ions.

(Concerning the mysterious-sounding "Cryptomelane-type manganese oxide", see:

Cryptomelane - Wikipedia, the free encyclopedia; "Cryptomelane is a potassium manganese oxide mineral".

And, with regards to "OMS-2" "molecular sieves", see the complete exposition of background concerning them authored in part by the University of Connecticut's Steven Suib a few decades ago, while he was still with Texaco, in: 

Manganese oxide octahedral molecular sieve as acid-base catalyst - Texaco Inc.; "United States Patent 5,523,509 - Manganese Oxide Molecular Sieve as Acid-Base Catalyst; 1996; Inventors: Chin-Lin O'Young, Robert Sawicki, Yan-Fei Shin, Steven Suib, NY and CT; Assignee: Texaco, Inc., NY; Abstract: Synthetic manganese oxide octahedral molecular sieves, e.g., OMS-1 and OMS-2, are employed as acid-base catalysts in a variety of acid-base organic conversion reactions".)

Claims:  A catalyst comprising manganese oxide-containing catalyst support material derived from manganese oxide-containing octahedral molecular sieves, at least one of iron carbide, cobalt carbide, and mixtures thereof, and an alkali metal (and) wherein the iron carbide comprises Fe3C (and) the cobalt carbide comprises Co3C (and) wherein the alkali metal comprises potassium, and is present in an amount ranging from about 4.0 wt. % to about 6.0 wt. % (and) wherein the catalyst further comprises cobalt carbide and copper, and the copper is present at Cu:Co molar ratio ranging from about 0.01:1 to about 0.5:1 (and) wherein iron carbide is present at a Fe:Mn molar ratio of no greater than 1:5 (and) wherein the alkali metal is present at an alkali metal:Mn molar ratio of no greater than 1:8 (and) wherein the alkali metal comprises potassium present as potassium hydrogen carbonate.

A catalyst comprising a manganese oxide-containing support material prepared by heat treatment of octahedral molecular sieves, at least one of iron carbide, cobalt carbide, and mixtures thereof, and an alkali metal (and) wherein the heat treatment comprises heating the octahedral molecular sieves to a temperature of at least 450 C in an atmosphere (and) wherein the atmosphere comprises of a mixture of H2 and either one of CO or CO2.

The catalyst ... wherein the heat treatment comprises heating the octahedral molecular sieves to a temperature and for a duration in an atmosphere sufficient to transform the octahedral molecular sieves to a mainly manganese oxide-containing support material (and) wherein the atmosphere comprises of a mixture of H2 and either one of CO or CO2.

(The catalyst is to be heat-treated prior to use, in other words, in a mix of gases that could be derived either from the gasification of Coal, as, for just one example, in: 

Celanese Co-Gasifies Coal and CO2-Recycling Algae | Research & Development | News; concerning: "United States Patent Application 20130144087 - Co-Gasification of Aquatic Biomass and Coal; 2013; Inventor: Dinesh Arora, Texas; Assignee: Celanese International Corporation, Irving, Texas; Abstract: The invention also relates to co-gasification processes for forming syngas from aquatic biomass and a fossil fuel. In one aspect, the invention is to a process for producing syngas, comprising: introducing aquatic biomass, a fossil fuel, water and oxygen to a gasifier and forming syngas comprising hydrogen, carbon monoxide and carbon dioxide; and feeding aquatic biomass with carbon dioxide derived from the syngas. In other aspects, the invention relates to integrated processes for producing industrial chemicals, such as alcohols, carboxylic acids, esters, aldehydes, olefins and polymers from such syngas. ...  Claims: A process for producing syngas, comprising: (a) introducing aquatic biomass, a fossil fuel, water and oxygen to a gasifier and forming syngas comprising hydrogen, carbon monoxide and carbon dioxide; The process ...  wherein the aquatic biomass is selected from the group consisting of microalgae, macroalgae, microplants, duckweed, water hyacinth, cattails, banana tree stem, kelp, and green algae (and) wherein the fossil fuel comprises coal";  

or, from a combined process that extracts both Hydrogen and Carbon Dioxide from the environment, as in:

US Navy Captures CO2 and Hydrogen for Hydrocarbon Synthesis | Research & Development | News; concerning: "United States Patent Application 20140238869 - Electrochemical Module Configuration for the Continuous Acidification of Alkaline Water Sources and Recovery of CO2 with Continuous Hydrogen Gas Production; 2014; Inventors: Felice DiMascio, Heather Willauer, Dennis Hardy, Frederick Williams, Kathleen Lewis; CT, VA, MD & PA; (Presumed eventual Assignee of Rights: The United States Navy)".) 

The catalyst ... wherein the iron carbide comprises Fe3C (or) wherein the cobalt carbide comprises Co3C (and) wherein the alkali metal comprises potassium, and ... wherein the potassium is present in an amount ranging an amount ranging from about 4.0 weight % to about 6.0 weight % (and) wherein the catalyst further comprises cobalt carbide and copper, and the copper is present at Cu:Co molar ratio ranging from about 0.01:1 to about 0.5:1 (and) wherein iron carbide is present at a Fe:Mn molar ratio of no greater than 1:5 (and) wherein the alkali metal is present at an alkali metal:Mn molar ratio of no greater than 1:8.

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.

Production of clean fuel and fine chemicals via Fischer-Tropsch ("FT") synthesis has attracted interest in both academia and industry.

Catalysts (Co, Fe, Ru, and Ni) for the conversion of CO2 supported on inert silica, alumina, zeolites, and carbon nanotubes have been developed for FT synthesis. The hydrocarbon products of these catalysts are mainly paraffins. Additional manganese oxides have been used to increase the selectivity towards long chain olefins, for instance, alkenes, but these manganese oxides decreased overall activity due to their enrichment on the catalyst surfaces.

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, C2-C6 carboxylic acids, .alpha.-hydroxylic acids, and their derivatives via CO2 and CO hydrogenation under different conditions".

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So, as officially confirmed just a few weeks ago by our United States Government, Honda Motor Company and The University of Connecticut collaborated in the development of a catalytic technology that will efficiently effect the "hydrogenation" of "CO2", perhaps "CO2" recovered via a process like that seen in: 

USDOE Hires WVU to Capture CO2 for Hydrocarbon Synthesis | Research & Development | News; concerning: "United States Patent 8,658,561 - Layered Solid Sorbents for Carbon Dioxide Capture; 2014; Inventors: Bingyun Li, et. al., West Virginia and Pennsylvania; Assignee: West Virginia University, Morgantown, WV; Abstract: A solid sorbent for the capture and the transport of carbon dioxide gas is provided having at least one first layer of a positively charged material that is polyethylenimine or poly(allylamine hydrochloride), that captures at least a portion of the gas, and at least one second layer of a negatively charged material that is polystyrenesulfonate or poly(acryclic acid), that transports the gas, wherein the second layer of material is in juxtaposition to, attached to, or crosslinked with the first layer for forming at least one bilayer, and a solid substrate support having a porous surface, wherein one or more of the bilayers is/are deposited on the surface of and/or within the solid substrate. A method of preparing and using the solid sorbent is provided. Government Interests: Certain embodiments of this invention were made with Government support in conjunction with the National Energy Technology Laboratory, Pittsburgh, Pa., under RES contract number DE-FE0004000 awarded by the U.S. Department of Energy. The Government may have certain rights in the invention";

and, perhaps using Hydrogen to effect the "hydrogenation" harvested via a process like that seen in:.

Penn State Solar Energy Extracts Hydrogen from H2O | Research & Development | News; concerning: "United States Patent Application 20140251819 - Methods for Hydrogen Gas Production; 2014; Inventors: Bruce Logan, et. al., PA, IL and South Korea; Assignee: The Penn State Research Foundation, University Park, PA; Abstract: According to aspects described herein, methods and systems provided by the present invention for hydrogen gas production include a RED (reverse electrodialysis) stack including one or more RED subunits, and use of a saline material including a heat regenerable salt. The salinity driven energy, provided by the one or more RED subunits, completely eliminates the need for an external power source to produce hydrogen gas";

and, which "CO2 ... hydrogenation" results in the synthesis of a range of hydrocarbons, including, and perhaps especially, "high value jet fuel".


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