United States Patent Application: 0150141238

If we were able to efficiently harvest the Carbon Dioxide byproduct co-generated by our use of Coal in the production of affordable and reliable electric power, or, from the atmosphere, as West Virginia University and the United States Department of Energy in our report of: 

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; 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 ... . 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. Studies have indicated that solid sorbents may have the potential to require substantially less energy (e.g. a reduction of 30-50%) for regeneration than the current MEA-based CO2 scrubbing processes. ... (The) fast CO2 desorption (exhibited by the materials and process of this invention) could make (these) sorbents a good option for CO2 removal from power plants and even the atmosphere";

confirm to be feasible, and, then, as seen in our report, from just this past May 8, 2015, of:

Kansas State University Converts CO2 into Gasoline | Research & Development | News; concerning the technical dissertation: "Carbon Dioxide Hydrogenation to Aromatic Hydrocarbons by Using an Iron/Iron Oxide Nanocatalyst; Hongwang Wang, et. al.; Kansas State University, Department(s) of Chemistry (and) Anatomy & Physiology, Analytical Imaging Laboratory (and) Department(s) of Biological and Agricultural Engineering (and) Chemical Engineering; Kansas, USA; June,  2014; Abstract: Being the most abundant carbon source in the atmosphere of Earth, CO2 can be used as an inexpensive C1 building block in the synthesis of aromatic fuels for internal combustion engines. We designed a process capable of synthesizing benzene, toluene, xylenes ... from CO2 and H2 at modest temperatures ...  employing Fe/Fe3O4 nanoparticles as catalyst. ... Earlier research showed that bulk iron and iron oxides catalyze CO2 hydrogenation, producing mainly (substitute natural shale gas) methane. ... Here, we report the selective formation of aromatic hydrocarbons from CO2 and H2 via a novel iron nanocatalyst. ... We have obtained evidence for the formation of aromatic hydrocarbons (benzene, toluene, xylenes and mesitylene) from carbon dioxide and hydrogen mixtures at 1 atm on Fe/Fe3O4 nanocatalysts. ... This technology is ... compatible with solar ... hydrogen technology and (can make) use of the existing distribution technology for gasoline";

convert that Carbon Dioxide, as Kansas State University, KSU, states to as well be feasible, into non-OPEC and  all-USA Gasoline, would that be a good thing?

KSU has, in fact, formally developed such catalytic technology, whereby harvested Carbon Dioxide can be reacted with elemental, molecular Hydrogen, in a reaction that can proceed at atmospheric pressure and modest temperatures, and be thereby converted into the hydrocarbons Benzene, Toluene and Xylene, aka "BTX", which, as explained and documented in that report of "Carbon Dioxide Hydrogenation to Aromatic Hydrocarbons", comprise the basic hydrocarbon blending stock from which Gasoline is directly formulated in conventional Gasoline manufacturing processes.

Hydrogen, as noted, in it's elemental, molecular form is needed for such CO2-to-Gasoline reactions; and, as seen in our report, for only one example, of:

USDOE 2014 Sunshine Extracts Hydrogen from Water | Research & Development | News; concerning: "United States Patent 8,729,798 - Anti-reflective Nanoporous Silicon for Efficient Hydrogen Production; 2014; Inventors: Jihun Oh and Howard Branz, CO; Assignee: Alliance for Sustainable Energy, LLC, Golden, CO(USDOE National Renewable Energy Laboratory); Abstract: Exemplary embodiments are disclosed of anti-reflective nanoporous silicon for efficient hydrogen production by photoelectrolysis of water. A nanoporous black Si is disclosed as an efficient photocathode for H2 production from water splitting half-reaction. Government Interests: The United States Government has rights in this invention under Contract No. DE-AC36-08GO28308 between the United States Department of Energy and the Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory. The photocathode ...  wherein the nanoporous black Si is configured to produce Hydrogen at about 20% above polished Si due to enhanced photon absorption in 1 sun illumination. A device comprising: an anti-reflective, nanostructured, black silicon photocathode configured for hydrogen production by photoelectrolysis of water";

our own United States Government now owns technology that will efficiently extract such needed Hydrogen from the abundant and renewable water, H2O, molecule in processes powered by low-grade, otherwise uneconomical and so-called "renewable", energy.

As we indicated in our earlier report concerning KSU's exposition of "Carbon Dioxide Hydrogenation to Aromatic Hydrocarbons", i.e., CO2-to-Gasoline technology, it seemed likely that further disclosures concerning KSU's process tor consuming CO2 in the synthesis of BTX, and thus Gasoline and other valuable hydrocarbon products, would eventually be forthcoming.

And, not long after that KSU dissertation was reported on by the West Virginia Coal Association, such "further disclosures" were, indeed, "forthcoming", as seen in excerpts from the initial link in this dispatch to:

"United States Patent Application 20150141238 - Nanoparticle Catalyst Capable of Forming Aromatic Hydrocarbons from CO2 and H2

NANOPARTICLE CATALYST CAPABLE OF FORMING AROMATIC HYDROCARBONS FROM CO2 AND H2 - KANSAS STATE UNIVERSITY RESEARCH FOUNDATION

Date: May 21, 2015

Inventors: Hongwang Wang, et. al., Kansas

Assignee: Kansas State University Research Foundation, Manhattan, Kansas

(As can be learned via:

20150141238 NANOPARTICLE CATALYST CAPABLE OF FORMING AROMATIC HYDROCARBONS FROM CO2 AND H2;

KSU seems to have simultaneously applied for an international patent on this CO2-to-Gasoline technology via the World Intellectual Property Organization.)

Abstract: Nanocatalysts and methods of using the same to obtain aromatic hydrocarbon compounds from a source of carbon atoms and a source of hydrogen atoms in a single reaction step is provided. The catalyst comprises an Fe/Fe3O4 (Iron/Iron Oxide) nanocatalyst that may be supported on a non-reactive support material such as a zeolite or alumina. CO2 and H2 are preferred sources of carbon and hydrogen atoms for the reaction. The aromatic hydrocarbon compounds produced are suitable for direct usage as fuel without need for further refining.

(Don't be thrown by the specification, as in the title, of "Nanoparticle". As can be learned via:

https://en.wikipedia.org/wiki/Nanoparticle and http://nanoparticles.org/;

"nanoparticle"s are known and understood. And, not only can they be worked with using modern processing equipment, "nanoparticles" of one material and another were even made and used, though described differently, as pigments for paint as long ago as the Middle Ages. This is stuff we know how to do. More about what size scales are being utilized can be learned via an informative article in the Forbes magazine:

http://www.forbes.com/sites/jimhandy/2011/12/14/how-big-is-a-nanometer/.)

Government Interests: STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH: This invention was made with U.S. Government support under grant number EPS-0903806 awarded by the National Science Foundation. The government has certain rights in the invention.

(http://www.nsf.gov/about/; "Where discoveries begin. The National Science Foundation (NSF) is an independent federal agency created by Congress in 1950 'to promote the progress of science; to advance the national health, prosperity, and welfare; to secure the national defense.'")

Claims: A method of synthesizing one or more aromatic hydrocarbon compounds comprising: providing within a reactor a quantity of a catalytic material comprising Fe/Fe3O4 core/shell nanoparticles; introducing into said reactor and contacting said catalytic material with a quantity of reactants comprising a source of carbon atoms and a source of hydrogen atoms; reacting said reactants within said reactor under conditions for forming said one or more aromatic hydrocarbon compounds; and recovering said one or more aromatic hydrocarbon compounds from said reactor.

The method ... wherein said source of carbon atoms comprises CO2 and/or CO.

(In fact, the full Disclosure also suggests "biomass", specifically "lignin", as another possible "source of carbon atoms". But, "biomass" isn't needed since "CO2 and/or CO" are perfectly acceptable sources of the needed "carbon" in this process. And, should Carbon Monoxide, "CO", for some reason be preferable to just Carbon Dioxide, CO2, then we remind you, that, as seen for only one example in our report of: 

Bayer Improves Coal + CO2 = Carbon Monoxide | Research & Development | News; concerning: "United States Patent 7,473,286 - Carbon Monoxide Generator; 2009; Assignee: Bayer Material Science, AG, Germany";

wherein the Bayer Corporation discloses how Carbon Monoxide can be efficiently manufactured with a high degree of purity by reacting Carbon Dioxide with hot Coal, the use of Carbon Monoxide in the process of our subject, "United States Patent Application 20150141238 - Nanoparticle Catalyst Capable of Forming Aromatic Hydrocarbons from CO2 and H2", can, as well, be seen as a route of Carbon Dioxide utilization. However, since molecular Hydrogen is utilized in this process, it seems likely that the Reverse Water Gas Shift reaction, as described in:

Reverse Water-Gas Shift Reaction - Marspedia; "The Reverse Water-Gas Shift Reaction (RWGS reaction) was discovered in the 19th century as a method of producing water from carbon dioxide and hydrogen, with carbon monoxide as a side product. ... CO2 + H2 = CO + H2O";

is as well occurring within this process, and, given sufficient Hydrogen, any Carbon Dioxide is being first converted into Carbon Monoxide on it's way to being consumed in the synthesis of Benzene, Toluene and Xylene, in any case. And, that fact is emphasized by KSU in the Summary section of the full Disclosure.)

The method ... wherein said reacting step within said reactor occurs at a pressure of between about 1 to about 1.1 atm.

(The above is very important. The CO2-to-Gasoline reaction can proceed at atmospheric pressure, and the reactor for conducting it can therefore be much less expensive to build than one in which high pressures would need to be maintained.)

The method ... wherein said reacting step ... occurs at a temperature of 380 C to about 560 C.

(The needed temperatures are a little on the high side, so there would be some energy consumption. However, some of the reactions involved are exothermic, and some of the needed heat to drive the entire process might come from some of the integrated individual reactions themselves.)

The method ... wherein said one or more aromatic hydrocarbon compounds recovered from said reactor are selected from the group consisting of xylenes, toluene, benzene, and mixtures thereof.

The method ... wherein said one or more aromatic hydrocarbon compounds recovered from said reactor are directly usable as a fuel in an internal combustion engine upon recovery from said reactor without under going further refinement

The method ... wherein said nanoparticles are supported on a non-reactive support substrate (and) wherein said non-reactive support substrate comprises a zeolite.

A method of synthesizing one or more aromatic hydrocarbon compounds comprising: providing within a reactor a quantity of a catalytic material comprising Fe/Fe3O4 core/shell nanoparticles; introducing into said reactor and contacting said catalytic material with a quantity of reactants comprising a source of carbon atoms and a source of hydrogen atoms, said source of carbon atoms being selected from ... CO2, CO, and combinations thereof, .... reacting said reactants within said reactor under conditions for forming said one or more aromatic hydrocarbon compounds, said conditions within said reactor comprise a temperature of between about 380 C to about 560 C, and a pressure of between about 1 to about 1.1 atm; and recovering said one or more aromatic hydrocarbon compounds from said reactor, said one or more aromatic hydrocarbon compounds being selected from the group consisting of xylenes, toluene, benzene, and mixtures thereof, said aromatic hydrocarbon compounds comprising at least 75% by weight of the total reaction products produced by said reacting step.

(In other words, "at least" three-quarters, "75%", of the product emerging from this Carbon Dioxide utilization process will be Gasoline blending stock, i.e., "xylenes, toluene, benzene, and mixtures thereof".)

A system for synthesizing one or more aromatic hydrocarbon compounds comprising: a reactor comprising a quantity of a catalytic material comprising Fe/Fe3O4 core/shell nanoparticles; one or more reactant feed streams coupled with said reactor and operable to deliver to said reactor a source of carbon atoms and a source of hydrogen atoms; said reactor operating under conditions for reacting said source of carbon atoms and said source of hydrogen atoms in the presence of said catalytic material for forming said one or more aromatic hydrocarbon compounds; and a reaction product discharge stream coupled with said reactor and operable to remove said one or more aromatic hydrocarbon compounds from said reactor.

The system ... wherein said reactor is a continuous reactor, and said source of carbon atoms comprises CO2, one mole of said catalytic material being capable of converting between 10,000 to 50,000 moles of CO2 into said one or more hydrocarbon compounds before the catalyst needs to be regenerated.

(The potential for using other sources of carbon, such as lignin or carbon monoxide, is repeated in other claims. But, the claim reproduced and highlighted above emphasizes and identifies what the process of our subject herein, "United States Patent Application 20150141238 - Nanoparticle Catalyst Capable of Forming Aromatic Hydrocarbons from CO2 and H2", is, really, actually all about.)

The system ... wherein said one or more aromatic hydrocarbon compounds removed from said reactor by said reaction product discharge stream are selected from the group consisting of xylenes, toluene, benzene, and mixtures thereof.

Background and Field: The present invention is generally directed toward nanocatalysts and methods of using such catalysts to synthesize aromatic hydrocarbon compounds from carbon dioxide and hydrogen mixtures under relatively mild reaction conditions. Particularly, the catalyst comprises an Fe/Fe3O4 nanocatalyst that may be supported on a non-reactive support material such as a zeolite or alumina. The aromatic hydrocarbon compounds produced are suitable for direct usage as fuel without need for further refining.

Being the most abundant carbon source in earth's atmosphere, CO2 can be used as a cheap and non-toxic C1 building block in many chemical processes.

Hydrogenation of CO2 to produce methanol and dimethylether (DME), as well as hydrocarbons is attractive, not only because these products are excellent fuels for internal combustion engines, but also because the whole process is considered to be cleaner, sustainable, and carbon-neutral (for example, using CO2 from atmosphere, H2 from water splitting and sunlight for energy).

Our distribution systems were developed for liquid fuel. It is easier and less costly to use the existing distribution infrastructure instead of building a new distribution system for methane or hydrogen. Liquid fuels are also safer than gaseous fuels: 1000 atmospheres (14,696 psi) of CH4 or H2 have the same density than 1 L of liquid fuels at room temperature. However, liquid fuels are much less in danger of explosion during accidents.

Although methane has a high octane number, it is not useful for classic combustion engines (and) whereas the long-term storage of hydrogen is very difficult, a mixture of aromatic hydrocarbons can be easily stored for fuel or synthesis application.

Iron-based heterogeneous catalysts have been intensively studied for the CO2 hydrogenation reaction. Earlier research showed that bulk iron or iron oxides catalyze CO2 hydrogenation, which mainly produce methane as product. These catalysts were rapidly deactivated due to carbon deposition. Doping of promoters such as potassium, manganese, and copper had significant effect on both the reactivity and selectivity of the iron-based catalysts. Higher olefins and aliphatic hydrocarbons, as well as improved CO2 conversion, were achieved. Al2O3 was found to be an excellent structure promoter to sustain the catalyst activity of iron-based catalysts by preventing sintering of active particles during the reaction. When using zeolites as solid supports, the product's distribution was highly dependent on the structure and acidity of the zeolites. The iron-zeolite composites were also reported as dual functional catalysts that promoted multi-step transformation for CO2 hydrogenation.

It is well accepted that the formation of aliphatic hydrocarbons from iron catalyzed CO2 hydrogenation reactions proceeds through a 2-step reaction process: first, conversion of CO2 to CO via the reverse water gas shift reaction (RWGS); and second, building up hydrocarbon chains by Fischer-Tropsch reaction."

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We'll close our excerpts there to emphasize again the importance of the above-specified "RWGS" reaction, which is integrated in the process of "United States Patent Application 20150141238 - Nanoparticle Catalyst Capable of Forming Aromatic Hydrocarbons from CO2 and H2" to convert the Carbon Dioxide into, first, Carbon Monoxide, on the way to synthesis of the "xylenes, toluene, benzene" Gasoline blending stock, as in "building up hydrocarbon chains by Fischer-Tropsch reaction".

That "Fischer-Tropsch reaction", we remind you, was developed in Germany prior to WWII in order to make liquid hydrocarbon fuels from Carbon Monoxide and Hydrogen, H2, manufactured by the gasification of Coal.

KSU seems to recommend "using CO2 from atmosphere, H2 from water splitting and sunlight for energy", as in the above excerpts, and, we remind you that, as in our reports of:

Efficient September, 2012, CO2 Air Capture | Research & Development | News; concerning: "United States Patent 8,273,160 - Method and Apparatus for Extracting Carbon Dioxide from Air; 2012; Abstract: A method and apparatus for extracting CO2 from air ... and for delivering that extracted CO2 to controlled environments. The present invention contemplates the extraction of CO2 from air using conventional extraction methods or by using one of the extraction methods disclosed; e.g., humidity swing or electro dialysis.  ...An apparatus for the capture of CO2 from ambient air"; and:

More NASA Hydrogen from Water and Sunlight | Research & Development | News; concerning: "United States Patent 4,051,005 - Photolytic Production of Hydrogen; 1977; Inventor: Nicholas Krascella, Connecticut; Assignee: United Technologies Corporation; Government Interests: The invention described herein was made in the course of a contract with the National Aeronautics and Space Administration. Abstract: Hydrogen and oxygen are produced from water in a process involving the photo-dissociation of molecular bromine with radiant energy at wavelengths within the visible light region (and) wherein the source of radiation is sunlight:";

we do indeed have such technologies for the harvesting of atmospheric Carbon Dioxide and the production of the needed Hydrogen in hand.

Herein, via publication of our subject, "United States Patent Application 20150141238 - Nanoparticle Catalyst Capable of Forming Aromatic Hydrocarbons from CO2 and H2", which discloses, in essence, how we can make Gasoline out of Carbon Dioxide, the good people out in Kansas have put the coffee on to brew. 

And, it's time the rest of us, all of us in United States Coal Country, indeed, all United States citizens, woke up and smelled it.


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