We've made a number of previous reports concerning the USDOE Oak Ridge, TN, National Laboratory scientists whose work we again address herein.
There might not be much conceptually new in this dispatch; but, it is becoming apparent to us that the work of these US Government employees, accomplished more than three decades ago, laid the technical foundations for some very recent developments; developments having what we see as rather immense technical implications for the potential of the United States of America to achieve a complete and total, and sustainable, self-sufficiency in terms of energy, and most specifically in terms of her supply of liquid and gaseous hydrocarbon fuels, with those fuels being derived from both Coal and Carbon Dioxide.
Those implications are rather enormously complex, and defy our admittedly handicapped efforts to provide you with a concise and accurate summary of them. So, for now, we'll stick with the basics and just plod along step-by-step.
First, as we've seen, for a few examples, in our reports of:
West Virginia Coal Association | England Recycles CO2 to Methanol | Research & Development; concerning: "United States Patent 3,950,369 - Methanol Production; 1976; Assignee: Imperial Chemical Industries Limited, London; Abstract: In a methanol production process synthesis gas containing carbon dioxide is passed over a methanol synthesis catalyst, cooled to remove part of the methanol and water contained in the gas, scrubbed with a liquid to remove substantially the remainder of the methanol contained in the gas, then recycled to the methanol synthesis catalyst. The process affords an economically significant increase in the rate of methanol recovery. (A) process for the production of methanol by passing a gas comprising hydrogen and carbon dioxide over a methanol synthesis catalyst which consists essentially of copper, zinc and ... chromium (or other specified) metal oxide";
and:
West Virginia Coal Association | USDOE Improves Direct Coal Hydrogenation and Conversion | Research & Development; concerning, in part: "United States Patent 5,015,366 - Process and Apparatus for Coal Hydrogenation; 1991; Assignee: The United States of America; Abstract: In a 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 is drained of excess water and dried at atmospheric pressure leaving catalyst deposited on the agglomerates. The agglomerates then are fed to an extrusion device where they are formed into a continuous ribbon of extrudate and fed into a hydrogenation reactor at elevated pressure and temperature. The catalytic hydrogenation converts the (Coal) extrudate primarily to liquid hydrocarbons in the reactor. ... Hydrogen is fed to (the) reactor ... after being compressed to reactor pressure ... and heated. The present invention provides several advantages over previously employed processes for conducting direct liquefaction of coal";
Hydrogen in it's elemental, molecular form can be used in some very direct processes for the conversion of both Coal and Carbon Dioxide into liquid fuels and hydrocarbons.
And, as we've seen in several previous reports, including, for just one example::
West Virginia Coal Association | USDOE Efficient Hydrogen from Water | Research & Development; concerning: "United States Patent 4,180,555 - Producing Hydrogen from Water Using Cobalt and Barium Compounds; December 25, 1979; Inventors: Carlos Bamberger and Donald Richardson, TN; Assignee: The United States of America; Abstract: A thermochemical process for producing hydrogen comprises the step of reacting CoO with BaO or Ba(OH)2 in the presence of steam to produce H2 ... . (The process) relates in general to the art of thermochemical hydrogen production. Thermochemical processes present the most attractive means for producing hydrogen. By this technique water is broken down into hydrogen and oxygen through a series of chemical reactions which do not involve the use of fossil fuels. Preferably, a series of reactions is carried out in a closed cyclic manner so that all products except hydrogen and oxygen are reused as reactants in other reactions, and the only reactant which must be added is water";
work, funded by our tax dollars, has been underway for quite a long time at the USDOE's Oak Ridge National Laboratory to develop efficient ways in which to utilize the simplest and most easily obtainable form of energy, heat, to split Water into Hydrogen and Oxygen, in cyclic processes that don't require the addition of anything in the form of raw materials but thermal energy and Water.
Herein, we present yet another, somewhat earlier, version of such Hydrogen production technology developed by the above Carlos Bamberger, and his colleagues, at the Oak Ridge National Laboratory, before the USDOE had actually been formed through the amalgamation of precedent government agencies; a version that continues to be cited by later developers of Coal and Carbon Dioxide hydrogenation technologies as supportive, precedent art.
Comment, with additional reference links, follows excerpts from the initial link in this dispatch to:
"United States Patent 3,996,343 - Process for Thermochemically Producing Hydrogen
Patent US3996343 - Process for thermochemically producing hydrogen - Google Patents
Date: December 7, 1976
Inventors: Carlos Bamberger and Donald Richardson, Oak Ridge, TN
Assignee: The United States of America
Abstract: Hydrogen is produced by the reaction of water with chromium sesquioxide and strontium oxide. The hydrogen producing reaction is combined with other reactions to produce a closed chemical cycle for the thermal decomposition of water.
(Neither the exotic-sounding "chromium sesquioxide" nor "strontium oxide" are all that expensive or hard to get; and, they're not actually used up, but are instead just cycled, in the process.)
Government Interests: This invention was made in the course of or under a contract with the Energy Research and Development Administration. It relates generally to the art of thermochemical hydrogen production.
Claims: A thermochemical process for splitting water to produce hydrogen, comprising the steps of:
- reacting (1) chromium sesquioxide with strontium oxide and water to produce strontium orthochromate IV and hydrogen as reaction products;
separating said hydrogen as a product of reaction;
- reacting (2) said strontium orthochromate IV and strontium hydroxychromate V with water to produce chromium sesquioxide, strontium chromate and strontium hydroxide as products;
reusing the thus produced chromium sesquioxide in said first mentioned step of reacting;
- reacting (3) said strontium chromate with a portion of said strontium hydroxide to produce strontium hydroxychromate V, water and oxygen as products;
separating said oxygen as a product;
- reusing said strontium hydroxychromate V as a reactant in said second mentioned step of reacting; and
- reusing the remaining portion of said strontium hydroxide to fulfill the strontium oxide requirement of said first mentioned step of reacting.
The process ... wherein said first mentioned step of reacting is carried out at a temperature within the range of 600 to 800 C.
The process ... wherein said third mentioned step of reacting is carried out at a temperature within the range of 80 to 100 C.
The process ... wherein said second step of reacting is carried out at a temperature within the range of 480 to 700 C.
(Some of the needed temperatures are high, but not nuclear reactor or blast furnace high. Electrical resistance heating, with electricity provided by a small, dedicated hydro or wind generation facility, or, in appropriate geographies, focused solar radiation, as Bamberger does specify in the full Disclosure to be an option, should easily do the trick.)
Background and Description: Conventionally, hydrogen has been produced from water by electrolysis. Electrolysis, however, is highly inefficient when considering the efficiency present in electricity production coupled with an efficiency of about 80 percent for electrolysis. Inherent in the electrolysis to produce hydrogen is the general futility of using one energy source typically fossil fuels at the point of electricity production to ultimately produce hydrogen at the point of electrolysis. The disadvantages and excess consumption of fossil fuels are obviously not overcome by such a process. Chemical processes for the direct conversion of fossil fuels and water into a hydrogen product are presently at the point of feasibility. These processes overcome many of the inefficiencies and disadvantages of electrolysis. These processes, however, still depend upon the use of fossil fuels in the energy scheme.
Thermochemical processes present the most attractive means for producing hydrogen. These processes normally involve a series of reactions which produce hydrogen from water. The reactions are desirably carried out in a closed cyclic manner such that all products except hydrogen and oxygen are reused as reactants. All thermochemical processes have as an object the direct utilization of heat from an energy producing facility such as a ... solar furnace.
Summary: It is thus an object of this invention to provide a novel hydrogen producing reaction.
It is a further object of this invention to provide a cyclic thermochemical process for splitting water into hydrogen and oxygen.
It is a still further object of this invention to provide such processes wherein no reactions are carried out at a temperature above 1300 K.
(In the full Disclosure, both the Centigrade/Celsius and Kelvin scales are, for some reason, used. The above "1300 K" would be just a tad hotter than 1000 C. If you read the full Disclosure, as accessible via the enclosed links, and feel the need to do the conversions, the necessary calculators can be accessed via:
Kelvin to Celsius conversion and Celsius to Kelvin conversion.)
These and other objects are accomplished by a process comprising the reaction of chromium sesquioxide and strontium oxide with water to produce hydrogen and strontium orthochromate IV. Additional combined reactions involving the hydrolytic disproportionation of the strontium orthochromate IV and strontium hydroxychromate V and the reaction of strontium hydroxide with strontium chromate VI to produce oxygen, strontium hydroxychromate V and water are utilized to result in a closed thermochemical process involving only three reactions."
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In essence, it's actually a fairly direct Hydrogen generation method, wherein the only things you have to add are heat and Water, with the effluents from the process being only Hydrogen and Oxygen, which Oxygen would be a commercial product of already broad utility, but which could be used in processes like that described in our report of:
West Virginia Coal Association | Conoco 2011 Coal + CO2 + H2O + O2 = Syngas | Research & Development; concerning: "United States Patent 7,959,829 - Gasification System and Process; 2011; ConocoPhillips Company; A system and process for gasifying carbonaceous feedstock ... thereby producing ... synthesis gas ... comprising (introducing) particulate carbonaceous material into a reactor lower section and partially combusting therein with a gas stream comprising an oxygen supply .... wherein said particulate carbonaceous material is ... coal (and) wherein said carrier liquid is selected from group consisting of water, liquid Carbon Dioxide, (or) mixtures thereof";
to help support the conversion of Coal and Carbon Dioxide into a hydrocarbon "synthesis gas"; and, thus, help to offset the costs of producing the Hydrogen.
However, we remind you that Bamberger took the concepts embodied by our subject herein, "United States Patent 3,996,343 - Process for Thermochemically Producing Hydrogen", and by our earlier-reported "United States Patent 4,180,555 - Producing Hydrogen from Water Using Cobalt and Barium Compounds", as cited above, even further; as seen in our report of:
West Virginia Coal Association | USDOE Hydrocarbon Syngas from CO2 and H2O | Research & Development; concerning: "United States Patent 4,313,925 - Thermochemical Cyclic System for Decomposing H2O and/or CO2 by Means of Cerium-Titanium-Sodium-Oxygen Compounds; 1982; Inventor: Carlos Bamberger, Oak Ridge, TN; Assignee: The USA as Represented by the USDOE; Abstract: A thermochemical closed cyclic process for the decomposition of water and/or carbon dioxide to hydrogen and/or carbon monoxide".
And, which "hydrogen and/or carbon monoxide" would constitute a hydrocarbon synthesis gas suitable for catalytic chemical condensation, as via the Fischer-Tropsch and related processes, into hydrocarbon gasses and liquids.
In passing, we note that the link we included in that dispatch, to the United States Patent and Trademark Office electronic file of "United States Patent 4,313,925" no longer functions properly. Here's a backup:
The complete suite of technologies, based on thermo-chemical conversions facilitated by metal oxide and other metal compound intermediates, developed by Bamberger and his USDOE colleagues have provided the basis for later, related, developments, some of which we have already reported to you, and others, established more recently, which we will address in the future.
In any case, if we decide we do need some Hydrogen, perhaps for beneficial use in a process like that described in our report of:
West Virginia Coal Association | US Navy Improves CO2 Hydrogenation Catalyst | Research & Development; concerning: "US Patent Application 20110105630 - Catalytic Support for use in Carbon Dioxide Hydrogenation; 2011; Assignee: The Government of the USA 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 process for hydrogenation of carbon dioxide and for making syngas comprising a ... RWGS (CO2 + H2 = CO + H2O) step which employs the catalyst composition of the present invention and products thereof. Claims: A catalyst support suitable for use in supporting a catalyst for hydrogenating carbon dioxide ... . (The product syngas) can subsequently be reacted over a heterogeneous catalyst to form hydrocarbons of desired chain length and type";
wherein Hydrogen is used, first, to convert, via the Reverse Water Gas Shift, "RWGS", reaction, Carbon Dioxide into Carbon Monoxide, and, second, to be reacted with the product Carbon Monoxide over a "catalyst to form hydrocarbons of desired chain length and type"; that is, a process whereby we could deliver a big old right and, then, a big old left, to, respectively, Cap and Trade taxes and OPEC, then, via the process disclosed by our subject, "US Patent 3,996,343 - Process for Thermochemically Producing Hydrogen", our own US Government has provided us with a seemingly economical way to get some.