United States Patent: 4051005

As should, by now, be apparent from all of our posts, the conversion of both Coal and Carbon Dioxide into hydrocarbons, into substances which can serve as Synthetic Petroleum and Substitute Natural Gas, as the products of such conversions are frequently labeled, requires that Hydrogen be somehow added to and combined with the Carbon that Coal and CO2 bring to the party.

That can in some cases be accomplished indirectly, as when Steam, H2O, is utilized in the gasification of Coal, as, for just one example, rather plainly stated in:

Texaco 1950 Coal + Steam = Hydrocarbon Syngas | Research & Development; which concerns: "United States Patent 2,516,974 - Gasifying Carbonaceous Material; 1950; Assignee: Texaco Development Corporation; The present invention relates to gasification of solid fuels and is more particularly concerned with the conversion of carbonaceous materials into a gaseous product ... composed primarily of carbon monoxide and hydrogen ... (which are) ... produced by the reaction of water vapor with carbon".



The above product blend of "carbon monoxide and hydrogen" is then suitable for subsequent catalytic condensation, via numerous, various and long-known processes, most often lumped generically under the label of "Fischer-Tropsch", into hydrocarbon liquids and gases.

Other, perhaps more efficient, Carbon hydrogenation technologies, as do most modern petroleum refineries in their upgrading, their "hydro-treating", of crude natural petroleum, require the supply and use of elemental Hydrogen for more direct, catalyzed hydrogenation reactions.

Such would include what should be a Coal Country public icon, West Virginia University's own "West Virginia Process" for the direct liquefaction of Coal, a portion of which technology is described in:

WVU Hydrogenates Coal Tar | Research & Development; which concerns: "Hydrogenation of Naphthalene and Coal Tar; Abhijit Bhagavatula; West Virginia University; 2009; 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. (Such hydrogenation produces Tetralin, which can then be used to enable and promote the) the direct reaction between coal and hydrogen (with the consequent)conversion of coal to refinable crude hydrocarbons, from which liquid fuels such as gasoline, diesel, kerosene, etc., can be produced".

Another would include the century-old, Nobel Prize-winning Sabatier process, now being made ready by NASA for use in making rocket fuel out of Carbon Dioxide on the planet Mars. As seen in:

NASA Rocket Fuel from CO2 | Research & Development; wherein we're told: "methane can be manufactured ... via the Sabatier process: Mix some carbon dioxide (CO2) with hydrogen (H), then heat the mixture to produce CH4 and H20 -- methane and water".

And, as we earlier documented, NASA has some thoughts about how we might, efficiently, produce such seemingly-valuable Hydrogen, as seen in yet another of our earlier reports:

NASA Hydrogen from Water and Sunlight | Research & Development; which makes disclosure of: "United States Patent 4,045,315 - Solar Photolysis of Water; August, 1977; Inventors: James Fletcher (pro-forma, we believe), Administrator, NASA; and, Porter R. Ryason; Abstract: Hydrogen is produced by the solar photolysis of water".

That NASA process for efficiently generating Hydrogen from Water unfortunately entails the use, as we pointed out, of an unpleasantly radioactive and, likely, hugely-expensive catalyst based on a salt of the element "Europium".

Even while they were developing their process of "United States Patent 4,045,315", however, NASA likely realized how unpalatable such a technique would be, and, through contract with one of their and the USDOD's prime suppliers of high technology, directed effort into finding an alternative way to make that needed Hydrogen from Water.

And, very soon after "United States Patent 4,045,315" was issued, they were acknowledged for having successfully done so.

As seen in our excerpts from the initial link in this dispatch to:

"United States Patent 4,051,005 - Photolytic Production of Hydrogen

Date: September, 1977

Inventor: Nicholas Krascella, Connecticut

Assignee: United Technologies Corporation, Hartford

Government Interests: The invention described herein was made in the course of a contract with the National Aeronautics and Space Administration.

Abstract: Hydrogen and oxygen are produced from water in a process involving the photo-dissociation of molecular bromine with radiant energy at wavelengths within the visible light region.

Claims: In the production of hydrogen from water the improvement which comprises: as an essential step thereof forming a water-halogen gas mixture and irradiating the mixture with radiation energy in the visible spectrum to form the corresponding hydrogen halide and processing the hydrogen halide to affect the release of hydrogen therefrom.

A process for producing hydrogen from water which comprises: forming a water-halogen gas mixture, dissociable in the presence of radiation in the visible spectrum; irradiating the water-halogen gas in mixture with radiation in the visible spectrum, forming the corresponding hydrogen halide and oxygen; separating the hydrogen halide from the oxygen; (and) processing the hydrogen halide to effect the release of hydrogen therefrom.

(And) wherein the source of radiation is sunlight.

A process for producing hydrogen from water which comprises: forming a water-bromine gas mixture at (specified conditions); irradiating the water-bromine gas mixture with radiation (as specified, and) forming hydrogen bromide and oxygen; separating the hydrogen bromide from the other species; forming a hydrogen bromide-iodine gas mixture; irradiating the hydrogen bromide-iodine gas mixture with radiation within the visible spectrum to form, in the reaction, hydrogen iodide; and decomposing the hydrogen iodide to effect the release of hydrogen therefrom.

Background and Summary: The present invention relates in general to photolytic processes and is directed, more specifically, to the production of hydrogen and/or oxygen from water utilizing a photolytic process.

The present invention involves a process for the production of hydrogen from water utilizing radiant energy within the visible light spectrum in a series of low-temperature photolytic or thermal reactions.

The overall reaction utilizes halogens, and ... (there) are many advantages to the invention and significant differences from the past technology including the following:

1. a source of high temperature heat is not required,

2. visible light is effective in promoting desired photolytic reactions such light being available from many sources including the sun,

3. optics or other concentrators are not required,

4. a large percentage of the total solar flux can be used to effect the reactions, and the products are easily separated."


In sum, as we understand it, the process, in step-wise fashion, so as to leverage the energy, first reacts Water with Bromine, thus freeing Oxygen and creating Hydrogen Bromide, then reacts the Hydrogen Bromide with Iodine, to create Hydrogen Iodide and regenerate the Bromine for more reaction with Water.

The Hydrogen Iodide can then, more easily, and with less expenditure of energy than would be the case with Hydrogen Bromide, be split apart, using "visible light" to regenerate the Iodine and produce Hydrogen.

Our read of it suggests that it is a very efficient process; and, even though Bromine and Iodine are "toxic", in that they are extreme irritants and corrosive of tissue, they aren't really "poisonous", or, worse, as with the Europium of "United States Patent 4,045,315", radioactive. And, they are readily and spontaneously deactivated, if need be, into harmless compounds.

Both can be, and commercially are, extracted from sea water; which likely helps to explain NASA's and United Technologies' focus on their use, since United Technologies is a major US Department of Defense contractor, as well, and has, as we've documented, participated in the development of Carbon Dioxide recycling technologies for the USDOD, some of which are seen, for just one example in our report:

US Navy Seeks More US and International CO2 Recycling Patents | Research & Development; which, in part, concerns: "US Patent Application 20110105630 - Catalytic Support for Use in Carbon Dioxide Hydrogenation; 2011;  Assignee: The Government of the US, as Represented by the Secretary of the Navy; Abstract: A process for hydrogenation of carbon dioxide and for making syngas".

Speculatively, the Hydrogen produced by the NASA-sponsored process herein, of "US Patent 4,051,005", could be utilized, as in the US Navy process of "US Patent Application 20110105630", to convert Carbon Dioxide, reclaimed from the environment, into "syngas", or, "synthesis gas", suitable for catalytic condensation into a variety of hydrocarbons, including liquid fuels, as definitively indicated in our report:

CO2 to Synfuel Production Ship | Research & Development; concerning: "US Patent 4,568,522 - Synfuel Production Ship; 1986; Assignee: Grumman Aerospace Corporation, NY; Abstract: A vessel, vehicle or aircraft is self-equipped with means for producing and storing synthetic fuel generated from the synthesis of carbon dioxide and hydrogen".

Which Hydrogen, as in the process of our subject "United States Patent 4,051,005 - Photolytic Production of Hydrogen", can be efficiently extracted, from Water, in a process that utilizes non-exotic and relatively inexpensive co-reactants; and, which, given that only "low-temperature photolytic or thermal reactions" are needed, can be driven entirely by freely-available "sunlight".

Finally, the whole point is, that, if we wish to convert both our abundant Coal and our freely-available Carbon Dioxide, through already-known and established technologies, into the hydrocarbon products we currently allow our nation to be extorted by largely-unfriendly foreign powers for the supply of; and, if we wish to do so using more efficient processes of direct hydrogenation, then we can do so by using  elemental Hydrogen extracted cheaply, via the process herein of  "US Patent 4,051,005", which uses only relatively common elements that can be extracted from sea salt as co-reactants; and, which use only freely-available Solar energy to drive the needed reactions.

All of that is, of course, unless, in our collective wisdom, we US citizens, especially we US citizens resident in US Coal Country, would prefer to remain as the fiefs of Big Oil, the lackeys of OPEC, and the stooges of the Environmental Lobby.

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