United States Patent Application: 0130331616

We've many times reported on the Carbon Dioxide utilization achievements of Nobel Prize-winner George Olah, and his colleagues, at the University of Southern California, as, for one example, in:

West Virginia Coal Association | Southern California Recycles More CO2 | Research & Development; wherein we documented, that, over the course of a decade, as in:

"United States Patent 7,608,743 - "Efficient and Selective Chemical Recycling of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products"; October, 2009; Inventors: George Olah and Surya Prakash, California; Assignee: The University of Southern California, Los Angeles; Abstract: An efficient and environmentally beneficial method of recycling and producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning powerplants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by chemical or electrochemical reduction secondary treatment to produce essentially methanol, dimethyl ether and derived products"; and:

"United States Patent 5,928,806 - Recycling of Carbon Dioxide into Methyl Alcohol; July, 1999; Inventors: George Olah and Surya Prakash, California; Abstract: A regenerative electrochemical cell system based on a fuel cell to oxidize methyl alcohol or other oxygenated hydrocarbons coupled with a regenerative cell to reduce carbon dioxide to form oxygenated hydrocarbons is disclosed. Methods to reversibly interconvert oxygenated hydrocarbons and carbon dioxide, to recycle carbon dioxide produced as a by-product of industrial processes, and to store and release electrical and chemical energy are also disclosed";

George Olah and his team, including the accomplished Surya Prakash, had steadily worked to improve, validate and expose the processes whereby Carbon Dioxide can be recycled into, for instance, the valuable and versatile fuel alcohol, Methanol, and into products which themselves can be derived from CO2-derived Methanol.

So efficacious are Olah's and his USC colleagues' techniques for converting Carbon Dioxide into alcohols and synthetic petroleum products, as in:

West Virginia Coal Association | US Gov Confirms Coal Can Be A CO2-Neutral Source Of Power | Research & Development; concerning:

"United States Patent 8,461,215 - Rendering Coal As An Environmentally Carbon Dioxide Neutral Fuel And A Regenerative Carbon Source; June 11, 2013; Inventors: George Olah and G.K. Surya Prakash, CA; Assignee: The University of Southern California, Los Angeles; Abstract: The invention provides a method for rendering coal as an environmentally essentially carbon dioxide-neutral fuel. Carbon dioxide produced from coal combustion is captured, purified, combined with coalbed methane or any other natural methane or natural gas source, or with hydrogen, and reacted under reaction conditions sufficient to form methanol and/or dimethyl ether, which can be used as fuel or feedstock for derived synthetic hydrocarbons and products";

our United States Government confirmed less than a year ago, that, by employing those technologies on a broad-enough scale, we could productively utilize all of the Carbon Dioxide co-produced by our Coal-fired power plants, and, thus, make "Coal ... An Environmentally Carbon Dioxide Neutral Fuel", while, we're tempted to add, creating a lot more Coal Country jobs and wrapping up OPEC's over-long tenure as our primary supplier of liquid hydrocarbon fuels in the process.

Note that Methane can be consumed and utilized as a co-reactant - - if preferred over elemental, molecular Hydrogen for whatever reason - - for these Carbon Dioxide-consuming processes. And, we'll note that we don't have to put our groundwater at risk by drilling and fracking for shale gas if we do wish to use the option of Methane, since, as seen, for only one out of many examples now, in our report of:

West Virginia Coal Association | USDOE Sunlight Converts CO2 into Methane | Research & Development; concerning: "US Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation;   March 28, 2013; Assignee: UChicago Argonne, LLC, Chicago; (Argonne National Laboratory, USDOE); Abstract: In one preferred embodiment, a photocatalyst for conversion of carbon dioxide and water to a hydrocarbon and oxygen ... . Government Interests: The United States Government has rights in this invention pursuant to Contract No. DE-AC02-06CH11357 between the United States Government and UChicago Argonne, LLC representing Argonne National Laboratory. Background and Field: This invention relates to the energy efficient photocatalytic conversion of carbon dioxide gas and water vapor to methane and other hydrocarbon fuels, particularly promoted by sunlight";

even our own US Government knows, that, in reactions powered by freely-available environmental energies, we can cleanly and efficiently make any Methane we might want for reactions with Carbon Dioxide out of nothing but Water and even more Carbon Dioxide.

But, Hydrogen can be used, as well, instead of Methane, in Olah's and Prakash's CO2-consuming technologies, and, as seen for just one example in:

West Virginia Coal Association | USDOE Renewable Energy Extracts Hydrogen from Water | Research & Development; concerning: "United States Patent 8,444,846 - Method and System for Producing Hydrogen Using Sodium Ion Separation Membranes; 2013; Assignee: Battelle Energy Alliance, LLC, Idaho Falls, ID; Abstract: A method of producing hydrogen from sodium hydroxide and water is disclosed. ... A system of producing hydrogen is also disclosed. Government Interests/Government Rights: This invention was made under a Cooperative Research and Development Agreement between Alberta Limited and Battelle Energy Alliance, LLC under Contract No. DE- AC07-051D14517, awarded by the U.S. Department of Energy. The U.S. Government has certain rights in the invention";

we're getting pretty good at generating Hydrogen in efficient ways, as well.

Why the US Government's confirmation of that fact, through their issuance, less than a year ago, of "United States Patent 8,461,215 - Rendering Coal As An Environmentally Carbon Dioxide Neutral Fuel And A Regenerative Carbon Source", the fact that we could start ushering OPEC out the door and toss the latest CO2 Cap & Trade Carbon Tax proposals in the wastepaper basket on our way down the hall, wasn't headline news in the printed media of US Coal Country remains something of a mystery that escapes us; but, it's a fact that hasn't yet lost the interest of Nobelist George Olah and of Surya Prakash out at the University of Southern California, as seen, via excerpts from the initial link in this dispatch, in the recently published:

"United States Patent Application 20130331616 - Recycling Carbon Dioxide via Capture and Temporary Storage to Produce Renewable Fuels and Derived Products

Patent US20130331616 - Recycling carbon dioxide via capture and temporary storage to produce ... - Google Patents

RECYCLING CARBON DIOXIDE VIA CAPTURE AND TEMPORARY STORAGE TO PRODUCE RENEWABLE FUELS AND DERIVED PRODUCTS - University of Sou

December 12, 2013

Inventors: George A. Olah and G. K. Surya Prakash, California

Assignee: The University of Southern California, Los Angeles

Abstract: A method for recycling a carbon-containing greenhouse gas emissions such as carbon dioxide and methane (natural gas) or a hydrocarbon homolog thereof. The method includes the steps of capturing the emissions, sequestering them in an underground or undersea storage area, withdrawing them from the storage area after storage therein, and converting them to carbon-containing compounds such as methanol, dimethyl ether and derived products. Greenhouse gases such as carbon dioxide and methane are chemically recycled to provide a permanent and inexhaustible supply of carbon-containing fuels or products, which subsequently can be combusted or used without increasing the carbon dioxide content of the atmosphere. The method is thus effective in neutralizing or reducing the carbon footprint due to human activities related to combustion or use of carbon-containing fuels while providing a repeatedly sustainable carbon source.

Claims: A method for controlling, neutralizing or decreasing the human carbon footprint of an entity by recycling carbon-containing gas emissions which have been captured and sequestered in an underground or undersea storage area, which method comprises withdrawing the gas from the storage area after sequestration or storage therein; and converting the gas to carbon-containing compounds to provide a renewable energy source while avoiding any unintended escape or release of the gas from the storage area, thus controlling, neutralizing or decreasing the carbon footprint of the entity.

The method ... wherein the renewed carbon-containing compounds are carbon-containing fuels or synthetic hydrocarbons (such as) methanol, dimethyl ether, or products derived therefrom.

(As we've documented many times, as, for one example in:

West Virginia Coal Association | ExxonMobil Coal to Methanol to Gasoline | Research & Development; concerning both:

"United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification; 1982; Assignee: Exxon Research and Engineering Company; Claims: A process for the production of methanol from a carbonaceous feed material (by)gasifying said carbonaceous feed material with steam ... and added hydrogen and carbon monoxide (and) wherein said carbonaceous feed material comprises coal"; and:

"United States Patent 4,035,430 - Conversion of Methanol to Gasoline"; 1977; Assignee: Mobil Oil Corporation;

Abstract: The conversion of methanol to gasoline";

one of the "products" which can be "derived" from "methanol", no matter which of our abundant natural resources, whether Coal or Carbon Dioxide, we make the Methanol from, is Gasoline.)

The method ... wherein the carbon-containing gas emissions are methane (and) wherein the carbon-containing gas emissions are used as the hydrogen source in the reductive conversion of carbon dioxide (dry reforming) or with a suitable combination with steam reforming (wet reforming) to provide a 1:2 molar mixture of carbon monoxide and hydrogen, which subsequently can react to produce exclusively methanol.

(In the above, Olah and Prakash are referring to what is also known as the "bi-reforming" or, if steam is added to the starting mix, sometimes as "tri-reforming" of Methane with Carbon Dioxide. That is a technology which was established before WWII, and which we've documented in numerous reports, such as, in one example disclosed by Olah and Prakash themselves, seen in our report of:

West Virginia Coal Association | California 2013 CO2 + Methane = Methanol | Research & Development; concerning: "United States Patent 8,440,729 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane; May 14, 2013; Inventors: George Olah and G.K. Surya Prakash, CA; Assignee: University of Southern California; Abstract: The invention provides for a method of forming methanol by combining a mixture of methane, water and carbon dioxide under specific reaction conditions ...to form a mixture of hydrogen and carbon monoxide which are then reacted ... to form methanol".

Futher, and again, and as further explained by the University of Southern California, in our report of:

West Virginia Coal Association | California Sunshine Converts CO2 into Methane for USDOD | Research & Development; concerning: "United States Patent Application 20130118906 - Method and System for Enhancing Catalytic and Photocatalytic Processes; May 16, 2013; Inventors: Stephen Cronin, et. al., California; Assignee: University of Southern California, Los Angeles; Abstract: A system for solar energy conversion includes a photoelectric cell. The photoelectric cell includes a cathode and an anode comprising a nanostructure array. The nanostructure array includes a semiconductor photocatalyst; and a plasmon resonant metal nanostructure film arranged on the semiconductor photocatalyst. The system is used in a method to produce methane by placing a photocatalytic cell in an environment containing CO2; and exposing the photocatalytic cell to visible light thereby allowing the CO2 to be converted to methane";

we can make any needed Methane - - to be reacted with Carbon Dioxide - - in processes driven by freely-available environmental energy, such as sunlight, i.e., "visible light", out of Carbon Dioxide)

The method ... wherein the carbon-containing gas emission is carbon dioxide (and) wherein the carbon dioxide is emitted from combustion or use of carbon-containing fuel (and) the carbon dioxide is captured from flue or off-gases of coal or other fossil fuel burning plants, geothermal power facilities, cement, aluminum or other industrial plants or factories, industrial or agricultural wastes or byproducts of natural gas production.

The method ... wherein the carbon dioxide is captured from the air or atmosphere (and) which further comprises adsorbing atmospheric carbon dioxide on an adsorbent and treating the adsorbent to release the adsorbed carbon dioxide therefrom.

(The University of Southern California and George Olah, as seen in our report of:.

West Virginia Coal Association | California Captures CO2 for Conversion to Hydrocarbons | Research & Development; concerning: "United States Patent 7,795,175 - Absorbents for the Separation of CO2 from Gas Mixtures Including the Air; 2010; Inventors: George Olah, et. al., CA; Assignee: University of Southern California, Los Angeles; Abstract: The invention relates to regenerative, supported amine sorbents that includes an amine or an amine/polyol composition deposited on a nano-structured support such as nanosilica. The sorbent provides structural integrity, as well as high selectivity and increased capacity for efficiently capturing carbon dioxide from gas mixtures, including the air. The sorbent is regenerative, and can be used through multiple operations of absorption-desorption cycles";

have themselves established the needed technology to capture CO2 from "the air or atmosphere".)

The method ... which further comprises chemically converting the withdrawn carbon dioxide into methanol by hydrogenative reductive processes (and, which) further comprises dehydrating the methanol under conditions sufficient to produce dimethyl ether.

The method ... wherein the dimethyl ether is used as a substitute for diesel fuel, natural gas or LPG for household heating.

(We've noted/documented in other reports that "dimethyl ether", or just "DME", with some modification of processing equipment, can serve as a direct replacement for both Diesel fuel and LPG. Otherwise, it, like Methanol, can be converted into Gasoline.)

The method ...  which further comprises converting the methanol or dimethyl ether to ethylene or propylene in the presence of a suitable catalyst (and) which further comprises hydrating the ethylene or propylene to form ethanol, propanol or isopropanol.

(As we've also noted and documented in other reports, both Methanol and DME can be used in the synthesis of various polymers and polymer raw materials, "ethylene or propylene", wherein the CO2 consumed in the synthesis of the Methanol and DME would remain permanently, productively and profitably "sequestered". We'll note, that, for whatever reason, even though, as noted above in our citation of our report concerning USC's "United States Patent 7,795,175 - Absorbents for the Separation of CO2 from Gas Mixtures Including the Air", the University of Southern California knows how to extract Carbon Dioxide from the atmosphere itself for use in these hydrocarbon and chemical synthesis processes, they go on at some length herein about withdrawing and utilizing CO2 from places, underground or in the deep sea, where it had been "sequestered", no doubt at the expense of consumers of Coal-based electric power. That should stand as warning to all who might otherwise entertain CO2 "sequestation" schemes.)

Background and Field: The invention relates to recycling of sequestered carbon-containing gases by converting the gases to renewable fuels such as methanol and dimethyl ether, and products derived therefrom.

The invention relates to a method for recycling a carbon-containing exhausts such as carbon dioxide or methane or its homologs after their capture and sequestration (CCS) making them renewable while at the same time mitigating their environmental harm. The method comprises withdrawing the carbon containing gas from the storage or sequestration points and converting them to carbon-containing fuels and compounds. The method provides a safe, environmentally adoptable renewable energy source. The carbon-containing compounds are preferably synthetic hydrocarbons, such as methanol, dimethyl ether, or derivatives thereof. By converting such stored gas into carbon-containing fuels and compounds, there becomes less of a concern of the unintended escape of gas that could occur if the gas were otherwise subjected to such long term storage.

In an embodiment, the recycled carbon-containing gas is carbon dioxide emissions produced by the combustion or use of carbon-containing fuel, or carbon dioxide captured from flue or off-gases of coal or other fossil fuel burning plants, geothermal power facilities, cement, aluminum or other industrial plants or factories, industrial or agricultural wastes or byproducts of natural gas production. The recycled gas can also be carbon dioxide captured from the air or atmosphere, such as by adsorption on an adsorbent followed by treatment, e.g., heating, of the adsorbent to release the adsorbed carbon dioxide.

(You will note, in the full Disclosure, should you examine the full document, multiple mention made of Carbon Dioxide captured among the "byproducts of natural gas production". As we've documented a number of times, but won't dwell on here, "America's Clean Energy Alternative" is often contaminated with sometimes quite large percentages of Carbon Dioxide just as it sits in natural geologic reservoirs. What no one tells you is, that, when the natural gas contains enough CO2 to impact the economics of gas transmission, or the efficiency of its combustion, that Carbon Dioxide is simply stripped from the natural gas at somewhat centralized facilities and then just vented to the atmosphere.)

In an embodiment, carbon dioxide is captured and recycled to produce methanol by any suitable method such as by hydrogenative reductive processes. Methanol can be further reacted or processed to form dimethyl carbonate or dimethyl ether. Methanol and dimethyl ether also can be converted to ethylene or propylene by acidic-basic or zeolitic catalysis. Ethylene and propylene, in turn, can be converted to any hydrocarbon products such as ethanol, propanol or isopropanol, or higher olefins, or aromatics, or products therefrom, such as for use as feedstocks for chemicals or as transportation fuels. These can replace fossil fuel derived transportation and industrial fuels and feed-stocks."

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George Olah, Surya Prakash and the University of Southern California aren't really telling us anything new herein. As seen in our many previous reports concerning them and their many Carbon Dioxide utilization technologies, they have already amply demonstrated that Carbon Dioxide - - as it arises in only a small way, relative to some all-natural and un-taxable sources of it's emission, such as the Earth's inexorable processes of planetary volcanism, from our essential use of Coal in the generation of truly abundant and truly affordable electric power - - is a valuable, maybe even a precious, raw material resource.

We can reclaim Carbon Dioxide from whatever source most convenient to us, even the atmosphere itself, and, then, in combination with Hydrogen, which can be extracted from Water in processes driven by various forms of freely-available environmental energy, or, in combination with Methane, which can itself be made from Carbon Dioxide, we can efficiently convert that reclaimed Carbon Dioxide into conventional forms of "fossil fuel derived transportation and industrial fuels and feed-stocks".


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