USDOE Renewable Hydrogen for Coal-to-Oil and CO2-to-Alcohol

United States Patent: 9011651

To be blunt:

Only our blind and obstinate clinging to the mythologies and - - we, here, have become convinced - - to the blind and narrow politics of oil and energy shortages prevents us all from embarking on a new era of United States of America hydrocarbon fuel self-sufficiency, and of United States Coal Country full employment and economic prosperity.

As seen for just two examples in our reports of:

Exxon Hydrogen Converts Coal into Hydrocarbon Liquids and Gases | Research & Development | News; concerning:"United States Patent 4,561,964 - Catalyst for the Hydroconversion of Carbonaceous Materials; 1985; Assignee: Exxon Research and Engineering Company; Abstract: An improved hydroconversion process for carbonaceous materials ... The improved process ... wherein said carbonaceous material is a normally solid material (and) wherein said normally solid hydrocarbonaceous material is selected from the group consisting of coal, lignite and peat (and) wherein the hydroconversion is accomplished in the presence of molecular hydrogen. ...After the carbonaceous material conversion is completed, and the several products, separated, the gaseous product may be upgraded to a pipeline gas, a high purity synthesis gas, or the same may be burned to provide energy for the conversion process. Alternatively, all or any portion of the gaseous product may be reformed to provide hydrogen for the liquefaction process. ... The liquid product may be fractionated into essentially any desired product distribution and/or a portion thereof may also be used directly as a fuel or upgraded using conventional techniques. Generally, a naphtha boiling range fraction will be recovered and the naphtha fraction will be further processed to yield a high quality motor gasoline ... . ... Also, a middle distillate fraction may be ...upgraded for use as a fuel oil or as a diesel oil. "; and:

NASA 2014 CO2 to Methane | Research & Development | News; concerning: "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2014; Assignee: Precision Combustion, Inc., CT; Abstract:A Sabatier process involving contacting carbon dioxide and hydrogen ... so as to produce a product stream comprising water and methane. ... 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";

some methods for the direct and efficient conversion of our abundant Coal and our some-say too-abundant Carbon Dioxide into seemingly-desirable products like "gasoline", "diesel oil" and substitute, fracking-free natural gas "methane" have been established which require a supply of "molecular hydrogen".

And, as we've seen in past reports, concerning technical achievements like:

"United States Patent 4,442,211 - Method for Producing Hydrogen and Oxygen by Use of   Algae; 1984; Inventor: Elias Greenbaum, Oak Ridge, TN; Assignee: The   United States of America; Abstract: Efficiency of process for producing H2 by   subjecting algae in an aqueous phase to light irradiation is increased by   culturing algae which has been bleached during a first period of irradiation   in a culture medium in an aerobic atmosphere until it has regained color and   then subjecting this algae to a second period of irradiation wherein hydrogen   is produced at an enhanced rate. Claims:A method of producing H2 and O2 by use of algae and light"; and:

"United States Patent 4,476,105 - Process   for Photosynthetically Splitting Water; 1984; Inventor: Elias Greenbaum,   Oak Ridge, TN; Assignee: The United States of America; Abstract: The invention   is an improved process for producing gaseous hydrogen and oxygen from water.   The process is conducted in a photolytic reactor which contains a   water-suspension of a photoactive material containing a hydrogen-liberating   catalyst. The reactor also includes a volume for receiving gaseous hydrogen   and oxygen evolved from the liquid phase";

our United States Department of Energy, at the Oak Ridge, Tennessee National Laboratory, and in the person of USDOE scientist Elias Greenbaum, have been at work developing a variety of technologies that enable the efficient extraction of "molecular hydrogen" from the abundant water, H2O, molecule.

We're not including links to our prior reports concerning the above Hydrogen production technologies, since links to those reports were included in another of our reports concerning the advancement of such Hydrogen evolution technology by the USDOE's Elias Greenbaum; as in:

USDOE Efficient Hydrogen for Liquid Fuel Synthesis | Research & Development | News; concerning: "United States Patent Application 20120149789 - Apparatus and Methods for the Electrolysis of Water; 2012; Inventor: Elias Greenbaum; Assignee: UT-Battelle, LLC; Oak Ridge, TN; (UT-Battelle, LLC is a limited liability partnership between the University of Tennessee and Battelle Memorial Institute that manages the Oak Ridge National Laboratory for the United States Department of Energy.) Abstract: An apparatus for the electrolytic splitting of water into   hydrogen and/or oxygen ... . This invention was made with government support under Contract Number   DE-AC05-000R22725 between the United States Department of Energy and   UT-Battelle, LLC. The U.S. government has certain rights in this   invention.The method ...  wherein said electrolyzer is powered by a renewable   energy source (and) wherein said renewable energy source comprises solar   energy (or) wherein said renewable energy source comprises wind energy (and)   wherein said electrolysis method is coupled to a process that utilizes   hydrogen or oxygen gas. The method ...  wherein said process is a   Fischer-Tropsch process for the synthesis of liquid hydrocarbons. The method ...  wherein said process is a hydrogenation process".

And, in passing, to again affirm what, and how valuable, an "hydrogenation process" could be, we refer, for one example, to our report of:

US Navy 2014 CO2 to Jet Fuel | Research & Development | News; concerning: "United States Patent 8,658,554 - Catalytic Support for Use In Carbon Dioxide Hydrogenation Reactions; 2014; Inventors: Robert Dorner, Heather Willauer, and Dennis Hardy, IL, VA and MD; Assignee: The United States of America 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 catalyst support supporting a catalyst for hydrogenating carbon dioxide and thereby forming long chain hydrocarbons ... . One can envisage a process leading to jet fuel, where the needed carbon source is obtained by harvesting CO2 dissolved in the ocean (primarily in the form of bicarbonate) and hydrogen through the electrolysis of water".

in any case, just days ago, technical experts in the employ of our United States Government independently confirmed the technical validity of "United States Patent Application 20120149789 - Apparatus and Methods for the Electrolysis of Water" through their allowance and issuance of, as excerpted from the initial link in this dispatch:

"United States Patent 9,011,651 - Apparatus and Method for the Electrolysis of Water

Apparatus and method for the electrolysis of water - UT-Battelle, LLC

Date: April 21, 2015

Inventor: Elias Greenbaum, Knoxville, TN

Assignee: UT-Battelle, LLC, Oak Ridge

(Again: UT-Battelle, LLC is a limited liability partnership between the University of Tennessee and Battelle Memorial Institute that manages the Oak Ridge National Laboratory for the United States Department of Energy.)

Abstract: An apparatus for the electrolytic splitting of water into hydrogen and/or oxygen, the apparatus comprising: (i) at least one lithographically-patternable substrate having a surface; (ii) a plurality of microscaled catalytic electrodes embedded in said surface; (iii) at least one counter electrode in proximity to but not on said surface; (iv) means for collecting evolved hydrogen and/or oxygen gas; (v) electrical powering means for applying a voltage across said plurality of microscaled catalytic electrodes and said at least one counter electrode; and (vi) a container for holding an aqueous electrolyte and housing said plurality of microscaled catalytic electrodes and said at least one counter electrode. Electrolytic processes using the above electrolytic apparatus or functional mimics thereof are also described.

Government Interests: This invention was made with government support under Contract Number DE-AC05-000R22725 between the United States Department of Energy and UT-Battelle, LLC. The U.S. government has certain rights in this invention.

Claims: An apparatus for the electrolytic splitting of water into hydrogen and/or oxygen, the apparatus comprising: at least one lithographically-patternable substrate having a surface; a plurality of microscaled catalytic electrodes embedded in said surface, wherein said microscaled catalytic electrodes are either catalytic anode electrodes or catalytic cathode electrodes; at least one counter electrode in proximity to but not on said surface, wherein said counter electrode comprises at least one catalytic cathode electrode if said microscaled catalytic electrodes are catalytic anode electrodes, or said counter electrode comprises at least one catalytic anode electrode if said microscaled catalytic electrodes are catalytic cathode electrodes; means for collecting evolved hydrogen and/or oxygen gas; electrical powering means for applying a voltage across said plurality of microscaled catalytic electrodes and said at least one counter electrode, wherein said electrical powering means are independently addressable to each microscaled catalytic electrode and said at least one counter electrode; and a container for holding an aqueous electrolyte and housing said plurality of microscaled catalytic electrodes and said at least one counter electrode. 

The apparatus ... wherein said lithographically-patternable substrate is a rigid semiconducting substrate (and) wherein said semiconducting substrate is a silicon-containing substrate. 

The apparatus ... further comprising means for collecting evolved hydrogen and oxygen gas, wherein said means comprises a canopy trapping device positioned over said plurality of microscaled catalytic electrodes and a separate canopy trapping device positioned over said plurality of microscaled catalytic counter electrodes. 

The apparatus ... wherein said lithographically-patternable substrate possesses a first surface on which is disposed a plurality of microscaled catalytic anode electrodes, and a second surface on which is disposed a plurality of microscaled catalytic cathode electrodes, wherein said first surface faces into a first compartment in which oxygen is to be produced, and said second surface faces into a second compartment in which hydrogen is to be produced. 

The apparatus ... wherein said electrical powering means includes electrically-conductive bond pads and wiring connected to said electrodes (and) wherein said electrical powering means comprises at least one receiving coil in electrical communication with said microscaled catalytic electrodes, wherein said receiving coil includes means for producing electrical power wirelessly from a wireless transmission source (and) wherein said electrical powering means further comprises a rectenna.

"A rectenna is a rectifying antenna, a special type of antenna that is used to convert microwave energy into direct current electricity" - - We can transmit the needed electricity into this thing via microwaves, it seems, thus eliminating the need for complex wiring, etc.)

(Rectenna - Wikipedia, the free encyclopedia; "A rectenna is a rectifying antenna, a special type of antenna that is used to convert microwave energy into direct current electricity" - - We can transmit the needed electricity into this thing via microwaves, it seems, thus eliminating the need for complex wiring, etc.)

An apparatus for the electrolytic splitting of water into hydrogen and oxygen, the apparatus comprising: a first lithographically-patternable substrate having a first surface, and a plurality of microscaled catalytic anode electrodes on said first surface; a second lithographically-patternable substrate having a second surface, and a plurality of microscaled catalytic cathode electrodes on said second surface; means for collecting evolved hydrogen and/or oxygen gas; electrical powering means for applying a voltage across said plurality of microscaled catalytic anode and cathode electrodes, wherein said electrical powering means are independently addressable to each microscaled catalytic anode and cathode electrodes; and a container for holding an aqueous electrolyte and housing said plurality of microscaled catalytic anode and cathode electrodes. 

The apparatus ... wherein said microscaled catalytic anode and cathode electrodes are not separated by an ion-permeable barrier (or) are separated by an ion-permeable barrier. 

A method for producing hydrogen and oxygen gases from the electrolytic splitting of water, the method comprising charging an electrolyzer with an aqueous electrolyte, and electrically powering said electrolyzer to produce hydrogen and oxygen gases ... . 

The method ... wherein said electrolyzer is powered by a renewable energy source (and) wherein said renewable energy source comprises solar energy (or) wind energy. 

The method ... wherein said electrolysis method is coupled to a process that utilizes hydrogen or oxygen gas (and) wherein said process is a Fischer-Tropsch process for the synthesis of liquid hydrocarbons (or)  wherein said process is a hydrogenation process.

(Again, concerning the above, see, for just one example, our above-cited report concerning: "United States Patent 8,658,554 - Catalytic Support for Use In Carbon Dioxide Hydrogenation Reactions; 2014; Inventors: Robert Dorner, Heather Willauer, and Dennis Hardy, IL, VA and MD; Assignee: The United States of America 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 catalyst support supporting a catalyst for hydrogenating carbon dioxide and thereby forming long chain hydrocarbons ... . One can envisage a process leading to jet fuel, where the needed carbon source is obtained by harvesting CO2 ... and hydrogen through the electrolysis of water".)

Background and Field: The present invention relates, generally, to the field of hydrogen and oxygen gas production, and particularly, to water electrolysis devices and methods of use. 

The electrolysis of water produces hydrogen and oxygen gas without the production of toxic and environmentally unfriendly byproducts. Moreover, since the electrolytic method uses electricity as the power source, another advantage of the electrolytic process over hydrocarbon processes is its amenability in receiving electrical power from a renewable source, such as solar, wind, or hydroelectric power.

Description and Summary: In some embodiments, any of the electrolytic methods described above for producing hydrogen and/or oxygen is coupled to one or more processes that utilize hydrogen and/or oxygen gas. By being coupled to one or more processes that utilize hydrogen and/or oxygen gas, the electrolytic apparatus can be physically connected to one or more process operations where hydrogen and/or oxygen is utilized such that hydrogen and/or oxygen gas is transported directly from the electrolyzer into the one or more process operations. Alternatively, the electrolytic method can be coupled to one or more processes although the electrolytic apparatus is not physically connected to one or more of the process operations. For example, hydrogen and/or oxygen produced by the electrolytic apparatus can be collected in a container and transported to one or more process operations to be used therein. 

In a first set of embodiments, the electrolytic method described above is coupled to a Fischer-Tropsch (FT) process for the synthesis of liquid hydrocarbons ... .

The numerous conditions typically employed in the FT process ... are well-known in the art. According to methods of the art, hydrogen for the FT process is typically provided by gasification of a carbonaceous feedstock, most commonly coal gasification.

Since the H2/CO molar ratio generally produced by coal gasification processes is about 0.7, as compared to the ideal H2/CO molar ratio of 2 for FT processes, the H2/CO molar ratio produced by coal gasification processes is typically further adjusted by the water-gas shift reaction (i.e., CO+H2O=CO2+H2). However, the water-gas shift reaction is an energy intensive process requiring high temperatures and the use of copious amounts of metal catalyst. Therefore, at least one advantage in coupling the instant electrolysis process with the FT process is that hydrogen produced from the instant electrolysis process can be mixed into a syngas feedstock mixture produced by coal or biomass gasification to increase the H2/CO ratio while not relying on a water-gas shift reaction for this purpose. 

(The full Disclosure goes into more detail, as well, about other processes in which the Hydrogen can be utilized, such as in the making of fertilizer.) 

In (another) set of embodiments, the electrolytic method described above is coupled to a hydrogenation process. The hydrogenation process can be any process that uses hydrogen gas. For example, the hydrogenation process can be a coal liquefaction process for the production of liquid hydrocarbons. The numerous conditions typically employed in the coal liquefaction process (e.g., catalysts, temperatures, and pressures) are well-known in the art, e.g., the Bergius process.

Several other processes can make use of the hydrogen gas produced by the electrolytic process described above. For example, current large-scale methanol production generally relies on the reaction between carbon dioxide and hydrogen".

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We've reported on the above "Bergius process" for the direct liquefaction of Coal through reactions with Hydrogen many times, since, as seen in:

CoalTL Wins Nobel Prize - in 1931 | Research & Development | News; it won the Nobel Prize in chemistry for it's inventor, Friedrich Bergius, all the way back in 1931, and, as seen for one more example in: 

USDOE Improves Direct Coal Hydrogenation and Conversion | Research & Development | News; concerning: "United States Patent 4,735,706 - Process and Apparatus for Coal Hydrogenation; 1988; Inventor: John A. Reuther, McMurray, PA; Assignee: The United States of America; Abstract: In the coal liquefaction process, an aqueous slurry of coal is prepared containing a dissolved liquefaction catalyst. A small quantity of oil is added to the slurry and then coal-oil agglomerates are prepared by agitation of the slurry at atmospheric pressure. The resulting mixture of agglomerates, excess water, dissolved catalyst, and unagglomerated solids is pumped to reaction pressure and then passed through a drainage device where all but a small amount of surface water is removed from the agglomerates. Sufficient catalyst for the reaction is contained in surface water remaining on the agglomerates. The agglomerates fall into the liquefaction reactor counter currently to a stream of hot gas which is utilized to dry and preheat the agglomerates as well as deposit catalyst on the agglomerates before they enter the reactor where they are converted to primarily liquid products under hydrogen pressure";

such direct reactions between Coal and Hydrogen for the manufacture of "liquid products" have continued to be developed and improved upon over the decades, even by our United States Government. And, concerning the fact, that, "current large-scale methanol production generally relies on the reaction between carbon dioxide and hydrogen"; we remind you, again for just one example, of our report:

Japan CO2 to Methanol to Gasoline | Research & Development | News; concerning both:

"United States Patent Application 20130237618 - Process for Producing Methanol; 2013; Inventors: Tatsumi Matsushita, et. al., Japan; Assignee: Mitsui Chemicals, Inc., Tokyo; Abstract: An object of the invention is to provide a methanol production process which can efficiently produce methanol from carbon dioxide and hydrogen while suppressing loads to the global environment. The process for producing methanol of the invention includes a step (a) of reacting hydrogen and carbon dioxide with each other in a reactor in the presence of a copper-containing catalyst to produce a reaction mixture containing methanol ... . ... The present invention relates to a process for producing methanol from carbon dioxide and hydrogen as materials"; and:

"United States Patent Application 0130014430- Method for Generating Electricity and for Producing Gasoline from Methanol and System Therefore; 2013; Inventor: Masaki Iijima, Japan; Assignee: Mitsubishi Heavy Industries, Ltd., Tokyo; Abstract: A method for generating electric power and for producing gasoline from methanol, includes the steps of: synthesizing gasoline by reacting methanol under a catalyst; recovering heat generated from the gasoline synthetic reaction of methanol by cooling the reaction with coolant to vaporize the coolant; and generating electric power by using the coolant vapor produced in the heat recovery. The power generation step may include generating electric power with a plurality of steam turbines in series, e.g., a high-pressure turbine, a medium-pressure turbine, and a low-pressure turbine";

wherein it was disclosed how Methanol can be synthesized from Carbon Dioxide through reactions with Hydrogen, as produced so effectively by the process of our subject herein, the United States Department of Energy's "United States Patent 9,011,651 - Apparatus and Method for the Electrolysis of Water"; and, then, how the Methanol can be subsequently converted directly into Gasoline, along with some amount of co-produced "electric power", which co-product "electric power" could, conceivably, be directed back into the process of our subject, "United States Patent 9,011,651 - Apparatus and Method for the Electrolysis of Water", to supplement the specified "electrical power from a renewable source, such as solar, wind, or hydroelectric", thus producing even more Hydrogen to convert even more Carbon Dioxide into even more Methanol.

Of course, if we all prefer to remain the economically indentured servants of OPEC, and to have our economically essential generators of abundant and affordable Coal-based electric power shut down because of the Carbon Dioxide/global warming alarmism, as opposed to creating new industries and new jobs in United States Coal Country, all we have to do is continue doing what we've been doing: stubbornly ignoring the facts and keeping our mouths shut about them.