WV Coal Member Meeting 2024 1240x200 1 1

USDOE Pays for Improved California Hydrogen Production

United States Patent Application: 0120296092

As we try to emphasize from time to time, in the course of our reportage concerning the very real and quite practical technologies which exist for converting our abundant Coal and our, some say too abundant, Carbon Dioxide into anything, quite literally anything and everything, we now spend too many American dollars and far too many young American lives to keep ourselves supplied with from some of the more hostile regions of the world - - and from the avaricious nations of OPEC - - an economical, ready supply of Hydrogen is needed to make those Coal and CO2 conversion, hydrocarbon synthesis technologies as efficient and profitable for us as they can be.

We've seen in:

West Virginia Coal Association | WVU Hydrogenates Coal Tar | Research & Development; concerning: "Hydrogenation of Naphthalene and Coal Tar Distillate over Ni/Mo/Al2O3 Catalyst; Abhijit Bhagavatula; 2009; Abstract: The hydrogenation of naphthalene and coal-tar distillates has been carried out in a Trickle Bed Reactor, in which the liquid is allowed to flow through the catalyst bed in the presence of hydrogen. The operating conditions employed for the hydrogenation of naphthalene (were varied, and the results monitored, and a) unique peak for naphthalene was observed ... (as was) the peak for the hydrogenated product, tetralin (1,2,3,4 Tetrahydronaphthalene). the importance of alternate sources of fuel and chemical feedstocks. The process of converting solid coal to liquid is called liquefaction. Coal is liquefied by reacting with hydrogen. ... Therefore, the process of producing liquid fuels from solid coal necessitates increasing the ratio of hydrogen to carbon. This can be done either by removing carbon or by adding hydrogen. Direct liquefaction, the direct reaction between coal and hydrogen, involves the conversion of coal to refinable crude hydrocarbons, from which liquid fuels such as gasoline, diesel, kerosene, etc., can be produced"; and:

West Virginia Coal Association | US Navy Awarded September, 2011, CO2 Recycling Patent | Research & Development; concerning: "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2; Date: September, 2011; Assignee: The United States of America as represented by the Secretary of the Navy; Abstract: A method of: introducing hydrogen and a feed gas containing at least 50% carbon dioxide into a reactor containing a Fischer-Tropsch catalyst; and heating the hydrogen and carbon dioxide to a temperature of at least about 190 C to produce hydrocarbons";

that, a little elemental, molecular Hydrogen can help us to achieve some miraculous things.

And, as we've seen, for only one example, in our report of:

West Virginia Coal Association | USDOE Efficient Hydrogen for Liquid Fuel Synthesis | Research & Development; concerning: "United States Patent Application 20120149789 - Apparatus and Methods for the Electrolysis of Water; 2012; Assignee: UT-Battelle, LLC (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. Claims: An apparatus for the electrolytic splitting of water into hydrogen and/or oxygen (and) further comprising means for collecting evolved hydrogen and oxygen gas (and) wherein said electrolyzer is powered by a renewable energy source (and) wherein said said electrolysis method is coupled to a process that utilizes hydrogen (and) wherein said process is a Fischer-Tropsch process for the synthesis of liquid hydrocarbons";

our United States Government, via the USDOE, has been wise enough to invest a few of the hard-earned dollars they relentlessly extract from us on the development of efficient Hydrogen production technology, with an eye towards just such Coal and CO2 conversion technologies for hydrocarbon synthesis.

And, herein, we see that they continue to fund the development of such technology, and continue to focus on the extraction of Hydrogen from its most abundant, most obvious source: Water.

One advance comment: We need to get a chemist to explain this one to all of us Coal Country troglodytes. The chemical shorthand employed in the disclosure of the technology is blindingly obtuse. But, that doesn't make it any less real.

Additional comment follows and is inserted within excerpts from the initial link in this dispatch to:

"US Patent Application 20120296092 - Catalysts for Generating Hydrogen from Water

Molecular Cobalt Pentapyridine Catalysts for Generating Hydrogen from Water - The Regents of the University of California

Date: November, 2012

Inventors: Jeffrey Long, et. al., CA

Assignee: The Regents of the University of California, Oakland

Abstract: A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition including the moiety of the general formula. [(PY5Me2CoL]2+ where L can be H2O, OH -, a halide, alcohol, ether, amine, and the like. In embodiments of the invention, water, such as tap water or sea water can be subject to low electric potentials, with the result being, among other things, the generation of hydrogen.

Government Interests: The invention described and claimed herein was made in part utilizing funds supplied by the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, and the National Science Foundation under Contract No. CHE-0617063. The government has certain rights in this invention.

Claims: An organo metal complex of the ... formula: (as specified in the full, official printed patent application document).

(We are obliged to over-condense the one, single "Claim" of this application, as it appears in the US Patent and Trademark Office's web page version of the document. The use of chemical shorthand in the statement of the claim makes it absolutely unintelligible to all but technical initiates of the highest order. The official, printed version of the application, a facsimile of which should remain accessible via the secondary link above, presents, as foreword, fully two dozen illustrations concerning both the catalysts' various potential molecular structures and the energy demands of those various catalytic structures as they are applied in the generation of H2 from H2O. But, it presents no claims, at all. The bulk of the Application is given over to explanation of how it all works together, and, of the fact that it all goes to serve in lowering the costs of Hydrogen production, both by reducing energy demand and by replacing the precious metals specified as catalysts in earlier technologies with cheaper, but more complex, "organo metal" compounds.)

Background and Field: This invention relates generally to a new composition of matter and, more specifically, to a new molecular electro-catalyst composed of inexpensive and abundant metals, capable of generating hydrogen from neutral water under ambient conditions at high rates with minimal applied potential, in one embodiment the metal being cobalt.

(The above is key to the whole invention. Reasonably abundant and affordable "cobalt", in combination with organic chemical structures, is used in place of much more expensive precious metal catalysts, with an additional benefit being that such a, relatively, inexpensive catalyst actually performs better in terms of lowering the amount of electricity needed to electrolyze, and produce Hydrogen from, the H2O.)

Owing to ... accelerating global energy demands, the search for viable carbon-neutral sources of renewable energy is amongst the foremost challenges in science today. One such alternative is hydrogen, which ... industries also use hydrogen as a reactant (an example being) the Haber-Bosch process that produces ammonia, which currently relies on steam reforming of natural gas or liquefied petroleum for the production of hydrogen. This is expensive, environmentally unsustainable (based on finite resources of fossil fuel and produces carbon dioxide and hydrogen sulfide, two major atmospheric pollutants) and necessitates removal of sulfur which deactivates the catalyst used for ammonia production. Hydrogen is also used as a reducing agent for metal ores, for the production of hydrochloric acid and as a hydrogenating agent for unsaturated fats and oils.

(Since) hydrogen has emerged as ... a precursor to many essential compounds, an intense interest in creating artificial systems that utilize earth-abundant catalysts for efficient hydrogen production from water has developed. A major quest of this renewable energy research is the search for efficient catalysts for the production of hydrogen from water, which rely on cheap, earth-abundant elements (and) there ... remains a need for even cheaper, more efficient catalysts for the generation of hydrogen from water.

Summary: According to the invention, a set of robust molecular cobalt catalysts for the generation of hydrogen from water are described. This cobalt complex, supported by a parent pentadentate polypyridyl ligand PY5Me2, features high stability and activity and 100% Faradaic efficiency for the electrocatalytic production of hydrogen from neutral water, with a turnover number reaching 5.5 (x) 10,000 moles of H2 per mole of catalyst with no loss in activity over 60 hours. Further experiments demonstrate that the overpotentials for H2 evolution can be (further optimized). 

The rates of hydrogen production using these organo metal catalysts are at least one to two orders of magnitude higher than other known molecular cobalt electro catalysts in neutral aqueous media. The cost of cobalt is about 200 times lower than the cost of platinum, the current catalyst used for hydrogen production.

(Illustrated experimental) data ... establish that (one version of the) catalyst operates at close to 100% Faradaic efficiency, meaning that every electron goes toward H2 production without generation of wasteful organic byproducts.

(In sum, the invention comprises) new molecular cobalt complexes for robust, efficient, and active electrocatalytic H2 generation from neutral pH water without organic additives."

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The required electric potentials for the "electrocatalytic H2 generation from neutral pH water", as enabled by the catalyst of this invention seem plenty low enough to enable the use of sources of environmental energy, that is, wind, hydro, solar, that are modest in capacity. We shouldn't, in other words, need a new Hoover Dam to generate enough CO2-free juice to make this process worthwhile. We submit that it could, in fact, be coupled with, or be "plugged" into, a system like that described in our report of:

West Virginia Coal Association | Germany & Pennsylvania Hydrogen from Hydropower | Research & Development; concerning: "United States Patent 6,864,596 - Hydrogen Production from Hydro Power; 2005; Assignees: Voith Siemens Hydropower Generation GmbH and Incorporated, Germany and York, PA; Abstract: A turbine installation configured for large scale hydrogen production";

and therein maximize the amount of Hydrogen which can be produced from what might otherwise be marginal sources of hydro or wind power, which we have plenty of in US Coal Country, and thereby make practical on a meaningful scale processes like those described in our reports of:

West Virginia Coal Association | USDOE CO2 + Hydrogen = Methanol and Ethanol | Research & Development; concerning: "United States Patent 7,858,667 - Alcohol Synthesis from CO or CO2; 2010; 
Assignee: Battelle Memorial Institute, WA; ("United States Department of Energy; Pacific Northwest National Laboratory; Proudly operated by Battelle since 1965".) Abstract: Methods for producing alcohols from CO or CO2 and H2 utilizing a palladium-zinc (Pd--Zn) on alumina catalyst are described. A portion of this work was funded by the U.S. DOE ... under Contract DE-AC06-76RL01830. Claims: A method of synthesizing alcohols from CO or CO2 comprising: flowing a reactant gas mixture comprising H2 and CO or CO2 into contact with a catalyst; wherein the catalyst comprises a Pd--Zn alloy dispersed on alumina; and forming an alcohol or alcohols"; and:

West Virginia Coal Association | Texaco 1951 Coal Hydrogenation | Research & Development; concerning: "United States Patent 2,572,061 - Process for the Hydrogenation of Coal; 1951; Assignee: Texaco Development Corporation; (An) improved process ... for the production of oil from coal by reaction of powdered coal with hydrogen";

wherein both Carbon Dioxide and Coal can be efficiently and directly converted into the sorts of things we now squander our national wealth to purchase from other folks elsewhere in the world; folks who, more often than not, act as if they don't really care for us, for the United States of America, all that much.