United States Patent Application: 0130092549

As we've documented now in many reports, but as has sadly and inexcusably remained totally unreported openly and directly to us by either our commercial press or our government representatives, our United States Government, via primarily, but not only, the US Department of Energy, has been making what could well be - - if we were ever to be informed of them and empowered to utilize the advancements arising from them - - some worthwhile investments with our tax dollars.

 

The USDOE has been financing, through both their own national laboratories and various institutions of higher learning, the development of technologies whereby various forms of environmental energy, primarily solar light and heat, can, via processes that have become known generally as "artificial photosynthesis", be harnessed to drive the conversion of Carbon Dioxide, CO2, in combination with Hydrogen extracted from the Water molecule, H2O, into any and all sorts and forms of hydrocarbon fuels and chemicals; that is, into anything and everything we now mortgage our nation's and our grandchildren's futures to the alien powers of OPEC to keep ourselves supplied with in the here and now, and, into even more.

Among the USDOE-sponsored, solar-powered Carbon Dioxide utilization achievements are those that have been accomplished at the California Institute of Technology, about which we've reported, for example, in: 

USDOE 2013 Solar CO2 + H2O = Methanol + Methane | Research & Development | News; concerning: "United States Patent Application 20130256147 - Solar Fuels Generator; Date: October 3, 2013; Inventors: Nathan S. Lewis and Joshua Spurgeon, CA; (California Institute of Technology); Abstract: The solar fuels generator (as described). Government Interests: This invention was made with government support under DE-SC000493/T-105066 awarded by the Department of Energy. The government has certain rights in the invention. Claims: A solar fuels generator, ...The supply stream ... can also include or consist of a reactant (in addition to water, and, in some embodiments) CO2 serves as the reactant that is delivered to the photocathodes. Examples of the fuels that can be produced using this reaction in combination with the disclosed solar fuels generator include ... methanol, methane, ethanol".

More about such productive solar-powered Carbon Dioxide recycling is explained in:

The Development of Solar CO2-to-Fuel Generators | Research & Development | News; concerning a report made by one of the Cal Tech scientists responsible for the above "United States Patent Application 20130256147 - Solar Fuels Generator", i.e. : "An Integrated, Systems Approach to the Development of Solar Fuel Generators; Nathan S. Lewis; 2013; Two major technological challenges in the development of a sustainable, clean energy system are providing massive grid-scale energy storage and an ample supply of carbon-neutral, high energy-density, transportation fuels. (One) challenge is that 40% of current global transportation fuel is consumed in uses for which electrification is technically difficult, if not impossible, such as in heavy-duty trucks, ships, and aircraft. ... Chemical fuels are desirable for energy storage ... and could (fulfil) the need for high energy-density, carbon neutral, sustainable, transportation fuels. Hence a clear rationale exists to develop technology options that involve the conversion of sunlight, by far the largest energy source, directly into chemical fuels. One approach to address both of these technology development imperatives involves the development of artificial photosynthesis. In artificial photosynthesis, sunlight is directly converted, without the use of (or the limitations of) living systems, into a useful chemical fuel. ... Production of fuels directly from sunlight is thus inspired by natural photosynthesis, but has the mandate to provide far superior performance than photosynthesis. In this respect, “performance” is measured by the net annually averaged energy conversion efficiency to produce a useful chemical fuel in a scalable, cost-effective fashion. A fully artificial photosynthetic system would also not require arable land, potable water, or involve tradeoffs of land to be used either for food or for fuel production. It is clearly possible to construct fuel-producing, man-made, solar energy conversion system that outperforms natural photosynthesis on an efficiency basis. Once electrons ... with the required energetics are produced (via solar conversion), catalysts are generally needed to facilitate the efficient production of chemical fuels (such as) to reduce CO2 to CH3OH, etc.). ... For this reason, a key R&D opportunity in the development of a solar fuels generator system is the development of suitable membranes or alternative physical/chemical/mechanical product separation schemes for enabling a scalable, manufacturable solar fuels generator. ... In one embodiment, water is split into H2 and O2, but H2 is not necessarily the fuel that will be provided to the end-user. The H2 could be ... combined with CO2 from flue gas or otherwise using the reverse water-gas shift reaction, in conjunction with Fischer-Tropsch reactions, to produce liquid fuels for use in transportation applications".

Although indicated in the above "An Integrated, Systems Approach to the Development of Solar Fuel Generators", but not that clearly stated, is the fact, that, the procurement of elemental, molecular Hydrogen can be key to the chemical utilization of Carbon Dioxide, since, as explained in our report of: 

NASA Improves CO2 to Methane Conversion | Research & Development | News; concerning: "United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2012; Inventors: Christian Junaedi, et. al., Connecticut; 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 Interests: 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";

Hydrogen is a reactive enough element, that, with proper catalysis, it will chemically combine automatically with Carbon Dioxide, to form such seemingly-desirable stuff as substitute natural gas Methane. The reactions between Hydrogen and Carbon Dioxide, again when properly catalyzed, are so "enthusiastic", so to speak, that they generate exothermic heat energy that needs to be extracted from the reaction zone, and which heat can be productively used in other operations.

Thus, the efficient and economical extraction of elemental Hydrogen from H2O becomes of key importance in CO2 utilization technologies, if the end result of such CO2 utilization is desired to actually be products of genuine value and utility, such as the hydrocarbon fuels and chemicals we now allow ourselves to be extorted - - at such great peril to our national security and such great harm to our national prosperity - - by OPEC for the supply of.

And, herein, we learn that the Cal Tech scientists responsible for the above-cited CO2-to-Hydrocarbon process of "United States Patent Application 20130256147 - Solar Fuels Generator" have, as the result of efforts financed by the same USDOE contract, specifically disclosed what might be thought of and seen as a needed sub-component of that CO2 utilization process, the solar-powered generation of the needed Hydrogen - - keeping in mind that Hydrogen can be made to subsequently react automatically with Carbon Dioxide in one contiguous process - - from Water.

As seen, with comment appended, in excerpts from the initial link in this dispatch to:

"United States Patent Application 20130092549 - Proton Exchange Membrane Electrolysis Using Water Vapor as a Feedstock

PROTON EXCHANGE MEMBRANE ELECTROLYSIS USING WATER VAPOR AS A FEEDSTOCK - CALIFORNIA INSTITUTE OF TECHNOLOGY

Patent US20130092549 - Proton exchange membrane electrolysis using water vapor as a feedstock - Google Patents

April 18, 2013

Inventors: Joshua Spurgeon, Nathan Lewis and Philip Marcus, CA

Assignee: California Institute of Technology, Pasadena

Abstract: A light-driven electrolytic cell that uses water vapor as the feedstock and that has no wires or connections whatsoever to an external electrical power source of any kind. In one embodiment, the electrolytic cell uses a proton exchange membrane (PEM) with an IrRuOx water oxidation catalyst and a Pt black water reduction catalyst to consume water vapor and generate molecular oxygen and a chemical fuel, molecular hydrogen. The operation of the electrolytic cell using water vapor supplied by a humidified carrier gas has been demonstrated under varying conditions of the gas flow rate, the relative humidity, and the presence or absence of oxygen. The performance of the system with water vapor was also compared to the performance when the device was immersed in liquid water.

Government Interests: This invention was made with government support under DE-SC0004993/T-105066 awarded by the Department of Energy. The government has certain rights in the invention.

Claims: An illumination-driven apparatus, comprising: a separator having a first side and a second side opposite said first side, said separator configured to be permeable to an ionic reaction moiety and configured to be substantially impermeable to molecular moieties so as to separate a first molecular moiety present on said first side from a second molecular moiety present on said second side; an oxidation catalyst present on said first side of said separator, said oxidation catalyst configured to oxidize H.sub.2O to produce molecular oxygen; a reduction catalyst present on said second side of said separator, said reduction catalyst configured to reduce a substance to produce a chemical fuel; a source of water vapor, said water vapor permitted to contact said first side of said separator and said oxidation catalyst; and a light absorber configured to absorb illumination, configured to provide electrons at a voltage sufficient to drive a desired chemical half-reaction at said reduction catalyst, and configured to accept electrons so as to drive another desired chemical half-reaction at said oxidation catalyst, said light absorber and said separator in mechanical contact so as to form a monolithic structure.

The illumination-driven apparatus ... further comprising a first inlet port configured to permit the introduction of water vapor into said apparatus and a first outlet port configured to allow molecular oxygen to exit said apparatus (and) wherein said chemical fuel is (Hydrogen) H2 (or) wherein said chemical fuel is a carbonaceous fuel ... .

The illumination-driven apparatus ... wherein said light absorber configured to absorb illumination is configured to absorb illumination having an intensity of approximately 1 kilowatt per square meter or less. (and) wherein said illumination having an intensity of approximately 1 kilowatt per square meter or less is terrestrial solar illumination.

A method of generating a chemical fuel and molecular oxygen from a reaction medium containing water vapor, comprising the steps of: providing an illumination-driven apparatus (with an) oxidation catalyst configured to oxidize H2O to produce molecular oxygen; a reduction catalyst present on said second side of said separator, said reduction catalyst configured to reduce a substance to produce a chemical fuel; a source of water vapor, said water vapor permitted to contact said first side of said separator and said oxidation catalyst; and a light absorber configured to absorb illumination, configured to provide electrons at a voltage sufficient to drive a desired chemical half-reaction at said reduction catalyst, and configured to accept electrons so as to drive another desired chemical half-reaction at said oxidation catalyst, said light absorber and said separator in mechanical contact so as to form a monolithic structure; providing water vapor that contacts said first side of said separator and said oxidation catalyst; illuminating said light absorber; oxidizing H2O to molecular oxygen at said oxidation catalyst; permitting H+ ions to permeate said separator; and performing a reduction at said reduction catalyst to produce a chemical fuel comprising hydrogen.

(And) wherein said reduction catalyst is a catalyst that reduces CO2 to produce a carbonaceous fuel.

The method of generating a chemical fuel and molecular oxygen from a reaction medium containing water vapor ... wherein said illumination-driven apparatus further comprises a chamber configured to contain a reagent, said chamber configured to permit said reagent to contact said second side of said separator and said reduction catalyst; and said method further comprises the steps of: providing a reagent containing CO2 within said chamber; and performing said reduction step on a mixture of said reagent and said H+ ions to produce a chemical fuel comprising hydrogen and carbon.

The method of generating a chemical fuel and molecular oxygen from a reaction medium containing water vapor ... wherein said illuminating step uses illumination having an intensity of approximately 1 kilowatt per square meter or less  (and) wherein said illuminating step uses terrestrial solar illumination.

Background and Field: In the issue of Chemical Reviews published on Nov. 10, 2010, Arthur J. Nozik and John Miller wrote in an editorial that "[t]he direct conversion of solar photons to fuels produces high-energy chemical products that are labeled as solar fuels; these can be produced through nonbiological approaches, generally called artificial photosynthesis.

(We've cited the above estimable Dr. Nozik previously, and will be reporting on his work again in the future. For more information now, see:

NREL: About NREL - Arthur J. Nozik — Research Fellow Emeritus.)

The feedstocks for artificial photosynthesis are H2O and CO2, either reacting as coupled oxidation-reduction reactions, as in biological photosynthesis, or by first splitting H2O into H2 and O2 and then reacting the solar H2 with CO2 (or CO produced from CO2) in a second step to produce fuels through various well-known chemical routes involving syngas, water gas shift, and alcohol synthesis.

There is a need for improved systems and methods for electrolyzing water to generate molecular oxygen and a chemical fuel without resorting to electrical energy sources external to the electrolysis cell.

Summary: According to one aspect, the invention features an illumination-driven apparatus. The illumination-driven apparatus comprises a separator having a first side and a second side opposite the first side, the separator configured to be permeable to (ions) and configured to be substantially impermeable to (molecules, with) an oxidation catalyst present on the first side of the separator, the oxidation catalyst configured to oxidize H2O to produce molecular oxygen; a reduction catalyst present on the second side of the separator, the reduction catalyst configured to reduce a substance to produce a chemical fuel; a source of water vapor, the water vapor permitted to contact the first side of the separator and the oxidation catalyst; and a light absorber configured to absorb illumination, configured to provide electrons at a voltage sufficient to drive a desired chemical half-reaction at the reduction catalyst, and configured to accept electrons so as to drive another desired chemical half-reaction at the oxidation catalyst, the light absorber and the separator in mechanical contact so as to form a monolithic structure.

In one embodiment, the illumination-driven apparatus further comprises a first inlet port configured to permit the introduction of water vapor into the apparatus and a first outlet port configured to allow molecular oxygen to exit the apparatus (and) the chemical fuel is H2 (and, in) another embodiment, the chemical fuel is a carbonaceous fuel.

In one embodiment, the illumination-driven apparatus further comprises a chamber configured to contain a reagent, the chamber configured to permit the reagent to contact the second side of the separator and the reduction catalyst; and the method further comprises the steps of: providing a reagent containing CO2 within the chamber; and performing the reduction step on a mixture of the reagent and the H+ ions to produce a chemical fuel comprising hydrogen and carbon."

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There is quite a lot more to it, but, the complete disclosure of our subject, "United States Patent Application 20130092549 - Proton Exchange Membrane Electrolysis Using Water Vapor as a Feedstock", in essence, describes more fully the chemical process being transacted in, as in our previous report linked-to above concerning it:

"United States Patent Application 20130256147 - Solar Fuels Generator; Date: October 3, 2013; Inventors: Nathan S. Lewis and Joshua Spurgeon, CA; (California Institute of Technology); Abstract: The solar fuels generator (as described). Government Interests: This invention was made with government support under DE-SC000493/T-105066 awarded by the Department of Energy. The government has certain rights in the invention. Claims: A solar fuels generator, ...The supply stream ... can also include or consist of a reactant (in addition to water, and, in some embodiments) CO2 serves as the reactant that is delivered to the photocathodes. Examples of the fuels that can be produced using this reaction in combination with the disclosed solar fuels generator include ... methanol, methane, ethanol";

which is disclosure of the Solar-powered fuel synthesizer wherein Carbon Dioxide is consumed, along with Water as a co-reactant, and the "fuel comprising hydrogen and carbon" which is produced can be "methanol, methane" or "ethanol".

We remind you that these Cal Tech achievements represent only one prong of our USDOE's broad effort to develop CO2-consuming Solar fuel technologies. We've reported on other examples, as well, as in:

USDOE Hires Nevada to Photo-Convert CO2 into Fuels | Research & Development | News; concerning: "United States Patent 8,709,304 - Hydrothermal Synthesis of Nanocubes of Sillenite Type Compounds for Photovoltaic Applications and Solar Energy Conversion of Carbon Dioxide to Fuels; 2014; Assignee: University of Nevada; Government Interests: This invention was made with government support under Grant Number DE-EE0000272, awarded by the U.S. Department of Energy; the United States federal government, therefore, has certain rights in the invention".

Further, we remind you, that, since "methane" can be one of the products, in addition to "methanol", made from Carbon Dioxide via the technologies and processes of our subject, "United States Patent Application 20130092549 - Proton Exchange Membrane Electrolysis Using Water Vapor as a Feedstock" and the associated USDOE/CalTech process of "United States Patent Application 20130256147 - Solar Fuels Generator", as seen in:

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

we can then react that CO2-based Methane with even more Carbon Dioxide, as recovered from whatever handy source, and thereby make more Methanol.

And, as seen for one example in our report of:

ExxonMobil Coal to Methanol to Gasoline | Research & Development | News; concerning both:

"United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification; 1982; Assignee: Exxon Research and Engineering Company"; and:

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

once we have Methanol, no matter which of our abundant and precious natural raw material resources, whether Coal or Carbon Dioxide, we make it from, we can then convert that Methanol directly into the stuff we seem so willing to fight foreign wars and bury our grandchildren under a mountain of foreign debt to keep ourselves supplied with in the here and now.

Carbon Dioxide, as herein, is a valuable, even a precious, natural raw material resource.

And, although we, here, are certainly not qualified to make any judgements, it really seems to us that it's time for the people whose responsibilities might be seen to include the honest and open reportage of news to, and the education of, the United States public, and perhaps those especially with fiduciary ties to United States Coal Country, began to fully and openly fulfil those responsibilities.


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