0002533710 METHOD OF OBTAINING METHANE FROM ATMOSPHERIC CARBON DIOXIDE

Carbon Dioxide, as is co-produced in only a small way - - relative to some all-natural, un-taxable, and totally non-political sources of it's emission, such as the Earth's inexorable processes of planetary volcanism - - by our economically essential use of Coal in the generation of abundant, affordable and reliable electric power, can be seen and treated as a valuable raw material resource.

For just one example, as seen in our report of:

NASA 2014 CO2 to Methane | Research & Development | Newsconcerning: "US Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; April 29, 2014; Assignee: Precision Combustion, Inc., CT; Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen in a first reaction zone with a first catalyst bed at a temperature greater than a first designated temperature; feeding the effluent from the first reaction zone into a second reaction zone, and contacting the effluent with a second catalyst bed at a temperature equal to or less than a second designated temperature, so as to produce a product stream comprising water and methane. The first and second catalyst beds each individually comprise an ultra-short-channel-length metal substrate. An apparatus for controlling temperature in an exothermic reaction, such as the Sabatier reaction, is disclosed. Government Support: This invention was made with support from the U.S. government under U.S. Contract No. NNX10CF25P sponsored by the National Aeronautics and Space Administration. The U.S. Government holds certain rights in this invention";

even our own United States Government knows that Carbon Dioxide can be efficiently and directly consumed in a century-old, Nobel Prize-winning process that synthesizes substitute, fracking-free shale natural gas Methane.

Elemental, molecular Hydrogen is needed for CO2-to-Methane reactions like that described by NASA, though not for all CO2 utilization processes. And, we remind everyone that, as seen for one example in:  

North Carolina Sunshine Extracts Hydrogen from H2O for USDOE | Research & Development | News; concerning: "US Patent 8,524,903 - Ruthenium or Osmium Complexes and Their Uses as Catalysts for Water Oxidation; 2013; Inventors: Javier Jesus Concepcion Corbea, et. al., North Carolina; Assignee: The University of North Carolina at Chapel Hill; Abstract: The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules. Government Interests: This invention was made, in-part, with United States government support under grants numbered DE-FG02-06ER15788 and DE-SC0001011 from the Department of Energy. The U.S. Government has certain rights to this invention. ... The present invention generally relates to catalysts for water oxidation. 
Hydrogen is one of the most promising alternative energy sources. It can be obtained by electrolysis of water, which is environmentally friendly and efficient. However, the electrolysis of water is an energy intensive process, which is very expensive. On the other hand, 
photolysis, the splitting of water by light, presents an attractive alternative method of obtaining hydrogen. Additionally, light driven reduction of carbon dioxide by water to provide hydrocarbons or methanol may be another promising alternative to alternate energy sources. For both types of reactions, coupled water oxidation to oxygen is required. ... Therefore, there is a need in the industry for an efficient catalyst for the electrolysis or photo electrolysis of water to obtain hydrogen or water reduction of carbon dioxide to obtain affordable and sustainable alternative source of energy. ... (One) aspect of the invention describes methods of generating hydrogen (H2) and/or oxygen (O2) gases. The method comprises providing a catalyst described herein and adding the catalyst to an electrolytic media under a condition effective to generate hydrogen and/or oxygen.  Another aspect of the invention describes methods of generating methanol, hydrocarbons and/or oxygen (O2). The method comprises: providing a catalyst described herein and adding the catalyst to an electrolytic media under a condition effective to generate methanol, hydrocarbons and/or oxygen (O2).  In another embodiment, the method comprises exposing the photo-electrochemical cell described herein to light radiation to generate hydrogen and oxygen gases without the requirement of applying an external electrical potential";

we're getting pretty good in any case at extracting the needed Hydrogen, even specifically for such chemical conversion and "reduction of Carbon Dioxide", from the abundant water, H2O, molecule in processes driven by nothing more than solar energy, that is, sunshine.

The Sabatier-type, CO2-to-Methane reactions, as described by NASA in "US Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction", are exothermic; that is, they typically generate heat energy as a byproduct of the CO2-to-Methane reaction. And, as seen for one example in:

Switzerland Designs CO2-to-Methane Industrial Plant and Process | Research & Development | News; concerning: "International Application Number: PCT/EP2014/068896; Publication Number: WO/2015/055349; INTEGRATED PROCESS/PLANT FOR STORAGE OF CO2 BY CONVERSION TO SYNTHETIC NATURAL GAS; Applicant: Paul Scherrer Institut, Villigen, Switzerland; Inventors: Tilman J. Schildhauer, et. al., Switzerland and Germany; Abstract: It is the goal of the present invention to provide a method and a plant for a most efficient operation of the industrial operation thereby storing the CO2 generated by this industrial operation in a way that further processes benefit from the energy stored into the CO2 separated from the industrial operation (wherein the CO2 can be subjected to a conversion into another product, such as SNG (Synthetic Natural Gas). This goal is achieved according to the present invention by a method and a plant for storing CO2 stemming from an industrial process as synthetic or substitute natural gas, comprising: a) an industrial operation plant generating CO2 comprised in a flue gas; said industrial operation plant performing an industrial combustion or calcination process or metallurgical process; b) a CO2 separating unit for separating a CO2 containing gas mixture from the flue gas; c) an electrolysis unit for splitting water by electrolysis to produce H2 and O2; d) a methanation unit for converting the CO2 containing gas mixture and the H2 by a methanation reaction to a methane rich gas which can be used as or upgraded to synthetic natural gas. Therefore, the present invention forms an integrated process to combine the four steps (combustion and/or calcination of cement; CO2 separation; electrolysis to produce H2 and O2; methanation) in a synergetic way to solve both problems described above with a significantly higher efficiency than possible in non-integrated plants. It is therefore the goal of the present invention to provide a method and a plant for a most efficient operation of the industrial operation thereby storing the CO2 generated by this industrial operation in a way that further processes benefit from the energy stored into the CO2 separated from the industrial operation (wherein the CO2 can be subjected to a conversion into another product, such as methane, SNG or the like). With respect to the present invention (the above is accomplished by): a) separating a CO2 containing gas mixture from a flue gas stemming from an industrial combustion or calcination step or a metallurgical process; b) splitting water by electrolysis to produce H2 and O2; c) converting the CO2 containing gas mixture and the H2 by a methanation reaction to a methane rich gas which can be used as or upgraded to synthetic natural gas. In order to take advantage of the exothermic methanation reaction, the CO2-separation can be conducted in a scrubber unit and the heat of the methanation reaction can be at least partly used to regenerate a scrubbing liquid used in the scrubber unit. Alternatively, the CO2-separation is conducted in a temperature swing adsorption reactor and the heat of the methanation reaction is at least partly used to regenerate the sorbents used in the temperature swing adsorption reactor";

technology is being developed around the world not only to harvest the heat energy generated by those exothermic CO2-to-Methane reactions, but then to use that byproduct heat energy for other productive purposes.

In point of fact, that exothermic CO2-to-Methane reaction heat typically has to be extracted from such Sabatier-type methanation reactions, since the temperature can build to excess and either damage the catalyst or cause deposition of elemental Carbon, which fouls and plugs the catalyst beds.

There is another option. As typically catalyzed, the CO2 methanization proceeds vigorously, generating, as noted, high temperatures. However, there are compounds and metals which will catalyze and drive that reaction at a lower and slower rate than those typically specified, as by NASA in the above-cited "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction".

And, use of those catalysts enables the design of a simpler, perhaps less expensive, CO2-to-Methane reactor. Further, and importantly, it has been discovered now in Russia that some compounds which catalyze that CO2 methanation reaction, albeit at a lower rate, are also, or can be combined with, compounds which are at least moderately effective at absorbing Carbon Dioxide from atmospheric air, as opposed to industrial exhaust gases.

Even further, such catalysts and catalytic technologies can be combined with the principles outlined in the above-cited "US Patent 8,524,903 - Ruthenium or Osmium Complexes and Their Uses as Catalysts for Water Oxidation; 2013;... The University of North Carolina .... This invention was made, in-part, with United States government support under grants numbered DE-FG02-06ER15788 and DE-SC0001011 from the Department of Energy. ...The present invention generally relates to ... photolysis, the splitting of water by light (as) an attractive alternative method of obtaining hydrogen. Additionally, light driven reduction of carbon dioxide by water to provide hydrocarbons or methanol may be another promising alternative to alternate energy sources. For both types of reactions, coupled water oxidation to oxygen is required. ... Therefore, there is a need in the industry for an efficient catalyst for the electrolysis or photo electrolysis of water to obtain hydrogen or water reduction of carbon dioxide"; 

wherein all of the necessary processes, such as extraction of Hydrogen from water, can be powered in the first place by solar energy.

In fact, the catalysts specified herein by Russia will drive the CO2-to-Methane reaction, but only if they are warmed a bit by solar energy, and after they have captured a useful amount of Carbon Dioxide from the air. As seen in excerpts from the initial and following links in this dispatch to: 

"METHOD OF OBTAINING METHANE FROM ATMOSPHERIC CARBON DIOXIDE

Application Number: 2013143033/04; Publication Date: November 20, 2014

Inventors: Vladimir Sergeevich Derevshchikov, et. al., Russia

(No "Assignee of Rights" is named in this World Intellectual Property Organization, WIPO, document.  However, separate web-based information sources reveal that all of the named inventors are on the faculty of Russia's Novosibirsk State University and/or the staff of the Boreskov Institute for Catalysis, both of which were established in the 1950's and are associated institutions. See:

http://www.nsu.ru/; and, http://www.en.catalysis.ru/. For more information and background, refer to:

Novosibirsk State University - Wikipedia, the free encyclopedia; "Novosibirsk State University was founded in May 1959 in the USSR ... in a program of establishing a Siberian Division of the USSR Academy of Sciences. Novosibirsk State University is one of the most famous universities in Russia, although is somewhat young. The university is located 20 kilometers from the city of Novosibirsk, a cultural and industrial center of Siberia. The total number of students in the year 1999 was 5200".

Further, we are uncertain of the durability of WIPO links, especially since this publication has aged a bit. A more complete link to the document is:

https://patentscope.wipo.int/search/en/detail.jsf;jsessionid=8739F621106536CA9CB885ED2D9DF6E8.wapp1nA?docId=RU124153785&recNum=10&maxRec=524&office=&prevFilter=&sortOption=Pub+Date+Desc&queryString=FP%3A%28air+fuel+synthesis%29&tab=NationalBiblio .)

Abstract: FIELD: chemistry. SUBSTANCE: applied is a mechanic mixture of a thermally regenerated sorbent - carbon dioxide absorbent, which represents potassium carbonate, fixed in pores of titanium dioxide (of composition specified) and a photocatalyst for the process of methanation or reduction of a composition separated in the process of the carbon dioxide regeneration: (as specified, including 1 to 5 % platinum, 5 to 20% Cadmium Sulfide and Titanium Dioxide  - the remaining part to 100, the content of the photocatalyst in the mixture constitutes 10-50 wt %. EFFECT: method represents an energy effective method of obtaining methane from air carbon oxide, applies alternative renewable energy for the fuel synthesis.

0002533710 METHOD OF OBTAINING METHANE FROM ATMOSPHERIC CARBON DIOXIDE

(We're including additional links which should, repeat should, take you to different sections of the document.)

The present invention relates to a technology for obtaining methane from carbon dioxide, air.

The direct use of solar energy as the driving force of chemical processes can be widely used in solving the problems of environmental protection, as well as problems of chemical technology. Among them is an important task of recycling atmospheric carbon dioxide. ... The catalytic conversion of carbon dioxide into fuel in the future may be one of the basic directions in the synthesis of fuels and products - precursor chemicals, especially given dwindling reserves of fossil carbon-containing fuels. Therefore there is a need for the absorption of carbon dioxide from the atmosphere of the Earth and its catalytic processing into useful fuels, such as methane.

(It) was proposed to convert additional carbon dioxide that goes directly into the catalytic reaction zone during the desorption from the surface of the high temperature of the sorbent. Thus, the high-temperature carbon dioxide sorbent was used as a temporary hub CO2, and at the right time, when the conditions of the process, carbon dioxide is desorbed and is involved in a useful chemical process.

The essence of the invention consists in that in the desorption process with a low-temperature carbon dioxide sorbent almost simultaneously adsorbed to the photocatalyst by light and reacts with hydrogen to form a useful product - methane Sabatier reaction: CO2 + 4H2 = CH4 + 2H2O.

The hydrogen for the methanation reaction is prepared beforehand by electrolysis. It should be noted that the low-temperature mixture heated regenerated sorbent and the photocatalyst ... under the influence of solar radiation, focused and transmitted by a system of mirrors. Hydrogen for the methanation process can be obtained by electrolytic dissociation of water under the influence of an external electric field, creating a system which provides a solar cell.

(Concerning the immediately above, see, for one example:

General Electric 2010 Hydrogen from Sunlight and Water | Research & Development | News; concerning: "United States Patent 7,820,022 - Photoelectrochemical  Cell and Method of Manufacture; 2010; Inventor: Thomas McNulty and Lifeng Zhang, NY; Assignee: General Electric Company, NY; Abstract: A photoelectrochemical cell may include a cell housing defining an interior volume with a window affixed to the cell housing for allowing the passage of light into the interior volume of the cell. A polymeric film may be affixed within the interior volume defining an anterior compartment and a posterior compartment within the cell housing. A plurality of semiconductor particles embedded continuously within a through thickness of the polymeric film so that a first respective surface area of the plurality of semiconductor particles is exposed to the anterior portion of the cell and a second respective surface area of the plurality of semiconductor particles is exposed to the posterior portion of the cell. The membrane may be immersed within an electrolyte so that incident radiation on the semiconductor particles causes oxidation and reduction to occur within the cell to produce gaseous hydrogen and oxygen.

Further, we are again compelled to note that this is a computer-generated English translation from the original Russian. Grammar is imperfect and some sentences/statements are incomplete.)

An important task for the organization of such a complex system as a sorbent / photocatalyst is a selection of the stable and high-performance catalytic systems and reliable low-temperature sorption materials. As such photocatalytic systems for methanation process can be used photocatalyst representing titanium dioxide deposited on its surface and the metal cadmium sulfide platinum photocatalyst such as proposed in the patent application. In the prior art, a working area for the transfer of the photocatalyst in the visible light region of the spectrum must promote titanium dioxide semiconductor particles such as CdS or ZnO. Also, to save material as a carrier can be used cheaper silica gel, which is then applied to the titanium dioxide.

The concentration of carbon dioxide from the atmosphere - is also a key part of the proposed process, synthesis of methane. The main difficulty in the concentration of carbon dioxide is a process of separation from the air, since the content of CO2 in the atmosphere is only (about) 390 ppm .; In addition, existing methods of concentration CO2 from gas mixtures are often unsuitable for allocating CO2 from the air, as traditional types of absorbers (zeolites, activated carbons) tend to have significantly higher affinity to water than to CO2 , and greatly reduces its capacity in water-containing atmosphere. To reduce the moisture of cleaned gas mixtures and increasing the capacity of adsorbents based on zeolites for carbon dioxide in the number of patents is proposed to use pre-drying unit, installed in front of the adsorption with zeolite ... . However, this method of solving the problem leads to considerable complication of the process flowsheet.

(The automated translation facility does have trouble converting Russian to English, and much of the Disclosure can't be reproduced here since the translator in some sections gives up and simply reproduces the original text, which we think is written in what's known as the Cyrillic alphabet. Much will be clearer when a United State Patent Application is published, which we assume it will be.)

The task of (removing/converting) the carbon dioxide from the air to provide a conversion process CO2 to methane solved by a method of carbon dioxide concentration, wherein a thermally regenerable carbon dioxide absorbent, is potassium carbonate as set forth in the pores of the titanium dioxide;the concentration of carbon dioxide is carried out periodically by blowing air from the process of regeneration of the sorbent. ... The sorption CO2 from the atmosphere is carried out at 20-40 degrees C.

Regeneration of the adsorbent is performed by heating to a temperature of adsorber 150-250 degree C (using a) focused source of visible light. 

Evolved carbon dioxide from the sorbent immediately reacts with the hydrogen in the reactor at the surface of the photocatalyst is also irradiated with visible light.

The technical result - efficient and environmentally safe method of producing methane from carbon dioxide, air, reducing the atmospheric concentration of carbon dioxide, the use of alternative inexhaustible energy for the chemical synthesis of fuels.

Thus, a method desorption catalytic conversion of carbon dioxide from air to methane, wherein the absorption and desorption of CO2 are performed periodically by solid regenerable sorbent desorption of carbon dioxide is combined with a photocatalyst methanation stage, which can significantly reduce the cost of energy production methane, and use only the sun's energy for the entire process.

In this cycle unit for production of methane from carbon dioxide, air is divided into two stages:

1. Concentration of carbon dioxide from the air (the temperature of the adsorber 20-40 C) is achieved by blowing air through the reactor with a regenerable sorbent and the mixture of the photocatalyst.

2. After saturation of the carbon dioxide sorbent is carried thermal regeneration of the sorbent at a temperature 150-250 C, while the reactor is supplied quantity of hydrogen corresponding to the stoichiometry of the Sabatier process. Desorbed from the sorbent is regenerable CO2 reacts with the hydrogen on the surface of the photocatalyst to form methane. Further purification is carried out by a mixture of methane-containing impurity gases then pure methane ... undergoes storage in cylinders or by low pressure pipe reaches consumers. ... The cycles of concentration and regeneration / methanation repeatedly periodically repeated.

0002533710 METHOD OF OBTAINING METHANE FROM ATMOSPHERIC CARBON DIOXIDE

Claims:

1. A method of producing methane from atmospheric carbon dioxide, characterized in that a mechanical mixture of thermally regenerable sorbent - carbon dioxide absorbent which is potassium carbonate, fixed in the pores of the titanium dioxide (as specified) and a photocatalyst for the methanation process ... .

2.  A method ... characterized in that the sorption of the carbon dioxide from the atmosphere is conducted at a temperature of 20-40 degrees C.

3.  A method ... characterized in that the regeneration of carbon dioxide-desorption heat treatment is carried saturated sorbent - absorber at a temperature 150-250 degree C, evolved during regeneration the carbon dioxide reacts with hydrogen on the surface of the photocatalyst was irradiated with visible light.

4.  A method ... characterized in that the regeneration of the sorbent and methanation or photocatalytic reduction of carbon dioxide on the surface of the photocatalyst carried out simultaneously in one reactor as a source of energy using solar radiation.

5.  A method ... characterized in that the sorption of the carbon dioxide from the atmosphere is carried out batchwise processes with desorption of carbon dioxide and methanation".

------------------------------

The final reproduced claim, specifying "batchwise processes" seems counter to our introductory comments indicating that this could be a continuous process. However, in related discussions we can't reproduce here, it's been proposed that the processes of absorption and de-sorption can be conducted on a conveying device that moves the combined methanation catalyst and CO2 absorbent into and out of an area of air exposure and into and out of a CO2-extraction/methanation chamber.

Again, the catalysts specified herein by Russia are key to the process, enabling, as they do, the conversion of CO2 into Methane only when they are heated moderately by solar radiation, after they have performed an initial function of extracting CO2 from the air. Thus, arrangements for cooling the reaction are unnecessary and the design of the thing can be both simpler and , presumably, less expensive. 

One feature not represented in our excerpts is that this Russian process seems to yield a less-than 70 percent conversion of Carbon Dioxide into substitute natural gas Methane. That, as opposed to related technology, as in our report of:  

Phillips 66 Converts 100% of CO2 to Methane | Research & Development | News; concerning: "United States Patent 8,754,137 - Methanation Reaction Methods Utilizing Enhanced Catalyst Formulations and Methods of Preparing Enhanced Methanation Catalysts; 2014; Inventors: Scott Scholten, et. al., Texas and Oklahoma; Assignee: Phillips 66 Company, Houston; Abstract: Enhanced mixed metal catalysts are provided which allow high conversions of carbon dioxide to methane, in some cases up to about 100% conversion. Methods of preparing enhanced mixed metal catalysts comprise a series of steps involving combining nickel and chromium salts with a nucleation promoter in a base environment to form a gel, allowing the gel to digest to form a solid and a mother liquor, isolating the solid, washing the solid, drying the solid, and thermally treating the solid to form a nickel-chromium catalyst. Methanation processes using the catalysts are also provided. The enhanced mixed metal catalysts provide more efficient conversion and lower operating temperatures for carbon dioxide methanation when compared to conventional methanation catalysts. Additionally, these enhanced catalyst formulations allow realization of higher value product from captured carbon dioxide";

where up to 100 percent conversion can be achieved. The advantages of this Russian invention seem, again, to lie in the simpler design enabled by their specified catalyst;  which catalyst allows for both the employment of solar energy to drive the process and serves double-duty by acting as well as an absorbent of Carbon Dioxide "in the atmosphere". And, as opposed to similar solar-driven processes, like that disclosed in:

Japan Photosynthesizes More Methane from CO2 | Research & Development | News; concerning: "United States Patent 8,696,883 - Method for Reducing Carbon Dioxide; 2014; Inventors: Satoshi Yotsuhashi, Masahiro Deguchi, Yuka Yamada, Japan; Assignee: Panasonic Corporation, Osaka; Abstract: The present subject matter provides a method for reducing carbon dioxide with the use of a device for reducing carbon dioxide. The device includes a cathode chamber, an anode chamber and a solid electrolyte membrane. The cathode chamber includes a working electrode which includes a metal or a metal compound. ... The method ... wherein ... the device is left at a room temperature and under atmospheric pressure.  The method ... wherein: a metal wire is provided on the surface of the region, and not only the region but also the metal wire are irradiated with the light (and) wherein ... at least one of formic acid, carbon monoxide and methane is obtained";

the Russian process of our subject, "METHOD OF OBTAINING METHANE FROM ATMOSPHERIC CARBON DIOXIDE; Application Number: 2013143033/04", is, like the above-cited Phillips 66 process of "United States Patent 8,754,137 - Methanation Reaction Methods", more focused on the production of, specifically, substitute natural gas Methane.

But, finally, it is demonstrated once again:

Carbon Dioxide can be seen and treated as a valuable raw material resource, the proper use of which could lead to new industries and new jobs in US Coal Country.

We can reclaim Carbon Dioxide even from the air itself, and then, in one nearly-continuous process powered by various forms of Solar energy, convert that CO2 efficiently into synthetic natural gas Methane.

An important nation straddling the continents of Europe and Asia, as herein, now knows that to be true, and maybe it's time we all figured it out, and accepted the fact, as well.


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