United States Patent: 4180555
We've now documented for you many technologies which enable the efficient conversion of our abundant domestic Coal, and other, but renewable, carbon resources into liquid hydrocarbons; that is, into direct replacements for anything, quite literally anything, we currently debase our nation and mortgage our children's futures to keep ourselves supplied with by purchasing from OPEC.
And, perhaps it would be instructive to dwell on a concept embodied in that statement for a bit.
The phrase "addiction to foreign oil", with the others like it, in all it's variations, although now overused to the point where it's trite, so commonplace that it's almost meaningless and trivial, carries strangely a depth of implication and meaning that bears, should demand, contemplation; especially insofar as it applies to our need for oil from unpleasant and dangerous places like the Persian Gulf, where extraordinary expenditures of taxpayer money are needed to keep the US Navy on patrol to defend shipping lanes, in essence subsidizing Big Oil's shipment of product by supplying security services.
It is almost as if we, one nation, were like a reasonably prosperous suburbanite who had, through unhappy circumstance, become addicted to pain killers; and, at last, with our lawful prescriptions used up and expired, were compelled by blind need to drive, with a gun in the car for protection, to violence-ridden neighborhoods where we buy, at prices that demand we steal from our winter heating reserve and our children's college savings, the drugs we need and crave from immoral, treacherous and dangerous back-alley dealers.
It's ugly. But, we do it. We continue to do it. And, over time, it becomes routine; if not easy, then normal, unremarkable - - even when we sometimes have to pull out the pistol we have stashed in the glove compartment, to get past the occasional mugger or thug lurking in the shadows around our buy zone.
It's what we do. It's how we live. It's how we get by.
And, it's wrong.
Quitting ain't easy. It's hard work; and, it's hard on you. Things get worse before they get better.
But, the work can get done and things can, eventually, get better.
That hard work can't get done though, and things can't get better, ever, unless that work gets started; and, that work won't get started unless we know, and unless we're certain or at least have the faith, that it can be done, that things can get better.
And, how are we to know that, unless someone has the honesty, and the courage, to tell us?
For now, it seems that no one has that fortitude and strength of character it would take to risk the derision, and the alienation, that would come by stating the truth, repeating the truth, and sticking to it.
We are a nation of imported oil junkies, and, we are so addicted we are too willing to accept the lies we're told by all the enablers, who, for their own suspect purposes, either tell us we can't do it, or who just, in what they themselves - Coal Country press - should see as cowardly and shameful silence, don't say anything.
Diatribe behind us, we remind you that Coal can be efficiently and directly converted into hydrocarbons through both catalyzed and un-catalyzed reactions with elemental, molecular Hydrogen.
A sampler of such technologies is accessible via our report of:
West Virginia Coal Association | Oklahoma & New Jersey Direct Hydrogenation of WV & PA Coal | Research & Development; concerning:
"United States Patent 3,960,700 - Coal Hydrogenation to Produce Liquids; 1976; Assignee: Cities Service Company; Abstract: Crushed coal is mixed with hot hydrogen, at 500 to 1,500C. and 600 to 3,000 psig., in a reactor, and then, after a short reaction time, rapidly quenched. The total heat-up, reaction, and quench time is less than 2 seconds. This short residence time results in less gas production and less polymerization of the liquid components. A process of treating carbonaceous material with hydrogen, in the absence of added catalyst, (and, a) method of converting coal into liquid hydrocarbon"; and:
"United States Patent 3,997,423 - Short Residence Time Low Pressure Hydropyrolysis of (Coal); 1976; Assignee: Cities Service Company; Abstract: Crushed coal is mixed with hot hydrogen, at 500 to 1,500C and 0 to 250 psig., in a reactor, and then, after a short reaction time, rapidly quenched. The total heat-up, reaction, and quench time is less than 2 seconds. This short residence time results in a high yield of coal tars. A process of treating carbonaceous material with hydrogen, in the absence of added catalyst, to produce a yield of carbonaceous tars"; and:
"United States Patent 4,003,820 - Short Residence Time Hydropyrolysis of Carbonaceous Material; 1977; Assignee: Cities Service Company; Abstract: A process for treating carbonaceous material with hydrogen (and) for converting coal into fluid hydrocarbons"; and:
"United States Patent 4,012,311 - Short Residence Time Low Pressure Hydropyrolysis of (Coal); 1977; Assignee: Cities Service Company; Abstract: A process for treating carbonaceous material with hydrogen at low pressure ... in the absence of added catalyst, to produce a high yield ... of desirable long chain aromatic hydrocarbons from coal".
With, thus, the value of Hydrogen established, which Hydrogen, by the way, looms large in economic analyses of Coal liquefaction technologies and assessments performed by the USDOE and others, we remind you that our own USDOE has really already solved that problem in large part.
As seen, for example, in our reports 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; June 14, 2012; Inventor: Elias Greenbaum; Assignee: UT-Battelle, LLC; Oak Ridge, TN; (UT–Battelle - Wikipedia, the free encyclopedia; "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"; and:
West Virginia Coal Association | USDOE Hydrogen from Sunlight and Water | Research & Development; concerning: "United States Patent 4,476,105 - Process for Photosynthetically Splitting Water; 1984; Inventor: Elias Greenbaum; 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 development of efficient Hydrogen production technologies has been a consistent theme for our United States Department of Energy, and, a career for some USDOE scientists.
Another USDOE scientist seemingly devoted to the development of superior Hydrogen production technologies, one who, for a time at least, must have worked side-by-side with the above-cited Elias Greenbaum at the USDOE's Oak Ridge, Tennessee, National Laboratory, is one Carlos Bamberger; and, he was responsible for the development of some very intriguing H2O-splitting reactions, where Hydrogen wasn't the only thing he was after.
We'll leave that as vague as it is for now, and, herein, introduce one of his efficient methods for producing Hydrogen; one which is immediately precedent to those perhaps more intriguing reactions noted above, and, one which our expert, technically-astute US Patent examiners perhaps thought we should take some special notice of, since they elected to award it on Christmas Day.
Comment is inserted within and follows excerpts from:
"US Patent 4,180,555 - Producing Hydrogen from Water Using Cobalt and Barium Compounds
(Process for producing hydrogen from water using cobalt and barium compounds - The United States of America as represented by t )
Date: 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 and novel double oxides of Ba and Co having the empirical formulas BaCoO2.33 and Ba2CoO3.33. The double oxide can be reacted with H2O to form Co3O4 and Ba(OH)2 which can be recycled to the original reaction. The Co3O4 is converted to CoO by either of two procedures. In one embodiment Co3O4 is heated, preferably in steam, to form CoO. In another embodiment Co3O4 is reacted with aqueous HCl solution to produce CoCl2 and Cl2. The CoCl2 is reacted with H2O to form CoO and HCl and the CoO is recycled to the initial reaction step. The Cl2 can be reacted with H2O to produce HCl. HCl can be recycled for reaction with Co3O4.
(The "HCl" is hydrochloric acid. And, what's happening, only in part, herein, is that the HCl is used as a sort of "transition" material. Chlorine gas is reactively "strong" enough to pull Hydrogen away from water, to form Hydrogen Chloride, HCl, that is, hydrochloric acid; which in turn gives the Hydrogen up when it reacts with Cobalt/Barium Oxides to comprise one route of Hydrogen generation in this complex reaction sequence. More Hydrogen appears to be generated in the reaction of H2O, "steam" with the "BaCo(OH2)" and/or the Ba/Co double oxide. It's all pretty complicated, and we can't pretend to understand it fully ourselves, even though the bright high school kid who tried to explain it to us seemed to; but, the upshot is that the complex chemical interactions result in a much-reduced need for energy input to pry the Hydrogen free of the H2O, which is the basic Hydrogen source. Neither the Barium or Cobalt, nor the Chlorine, are consumed or physically used up in the process; and, none of them are that expensive to begin with, so it's all pretty efficient. Further, all that's really needed is heat energy, so technical complications necessitated by the use of electrolytic techniques and apparatus are eliminated.)
This invention was made in the course of, or under, a contract with the United States Department of Energy.
Claims: A process for producing hydrogen comprising the step of:
(a) reacting CoO with BaO or Ba(OH)2 in the presence of steam at a temperature above about 500C to produce H2 and a double oxide of Ba and Co.
(And) further comprising reacting said double oxide of Ba and Co with H2O to form Co3O4 and Ba(OH)2 (and) further comprising recycling said Ba(OH)2 to said step (a).
The process ... further comprising heating said Co3O4 to form CoO and recycling said CoO to step (a).
The process ... in which said Co3O4 is heated in the presence of steam.
The process ... further comprising:
(b) reacting said Co3O4 with aqueous HCl solution to produce CoCl2 and Cl2,
(Which should generate some Hydrogen, as well.)
(c) reacting said CoCl2 with H2O to form CoO and HCl, and
(d) recycling CoO from step (c) to step (a).
The process ... further comprising:
(e) reacting Cl2 from step (b) with H2O to produce HCl and O2
(f) recycling HCl from steps (c) and (e) to step (b).
(Note that Oxygen is a byproduct of the process, and may have commercial value to help offset costs.)
Description: It 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.
(The above is a critical factor, we think, and serves to make this, or a process like it, more worthy of consideration. The only raw material, the only consumable, required is Water.)
The chief considerations in thermochemical hydrogen production processes are the maximum heat required to drive the reaction, the ease of separation of the products, and the kinetics of the reactions. Since the inputs to the processes are thermal energy and water, the lower the reaction temperature, the lower is the cost of the product. The faster the kinetics of the reactions, the larger is the throughput through a plant, and consequently, the lower is the investment required per unit of output.
(The above figure into Bamberger's design of this thing. He balanced, from his perspective, "temperature" with the "kinetics", and thus "throughput", and came up with a combination of components to optimize the "investment required per unit of output". And, what he came up with is something that would work well, but maybe not so much in Coal Country, as we will explain.)
Summary: It is an object of this invention to provide a novel method for producing hydrogen utilizing barium and cobalt compounds.
It is a further object to provide novel compositions of matter comprising barium-cobalt double oxides useful as intermediates in the process.
It is a further object to provide a process for producing hydrogen which can be carried out in a closed manner such that the only inputs to the process are water and thermal energy.
It is a further object to provide a closed process wherein all reactions can proceed below about 950C."
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Now, truth to tell, "950C" is pretty hot; and, the minimum reaction temperature disclosed in the full Disclosure, though not reflected in our excerpts, is "600C"; which is still pretty hot.
There is, thus, some significant energy requirement for this process; and, it is likely a process probably best operated where an obvious form of concentrated heat energy can be extracted from the environment, much as seen in our reports of:
NASA Hydrogasifies Coal with Solar Power | Research & Development; concerning: "United States Patent 4,290,779 - Solar Heated Fluidized Bed Gasification System; 1981; NASA; Abstract: A solar-powered fluidized bed gasification system for gasifying carbonaceous material. The system includes a solar gasifier ... which is heated by fluidizing gas and steam. Energy to heat the gas and steam is supplied by a high heat capacity refractory honeycomb which surrounds the fluid bed reactor zone. The high heat capacity refractory honeycomb is heated by solar energy focused on the honeycomb by (the) solar concentrator ... . Back-up furnace is provided for start-up procedures and for supplying heat to the fluid bed reaction zone when adequate supplies of solar energy are not available"; and:
Solar Power Converts CO2, H2O and Coal to Hydrocarbon Syngas | Research & Development; concerning: "US Patent 4,177,120 - Photolytic Process for Gasification of Carbonaceous Material; 1979; Assignee: Solarco Corporation, Rockville (MD); Abstract: Process and apparatus are disclosed for converting carbon dioxide to carbon monoxide by subjecting the carbon dioxide to radiation in the presence of carbonaceous material such as coal to form carbon monoxide. The preferred form of radiation is solar energy, and the process is preferably carried out in an atmosphere essentially free of oxygen".
But, that doesn't mean the technology shouldn't be of interest to us here in the cloudy heart of US Coal Country.
First, we could export Coal to Florida, where they would still need Solar concentrators, which are available, so that someone could operate the process of the above "United States Patent 4,177,120 - Photolytic Process for Gasification of Carbonaceous Material" in concert with the process of our subject, "United States Patent 4,180,555 - Producing Hydrogen from Water Using Cobalt and Barium Compounds", and thus make both the Hydrogen and the Carbon Monoxide required for:
Fischer–Tropsch process - Wikipedia, the free encyclopedia; "The Fischer–Tropsch process ... is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. The process, a key component of gas to liquids technology, produces a synthetic lubrication oil and synthetic fuel, typically from coal".
Second, since, as seen in:
West Virginia Coal Association | Grumman Aerospace Recycles CO2 | Research & Development; concerning: "United States Patent 4,282,187 - Hydrocarbons from Air, Water and Low Cost Electrical Power; 1981; Assignee: Grumman Aerospace Corporation; Abstract: A process for manufacturing synthetic hydrocarbons such as gasoline and/or kerosene from the synthesis of carbon dioxide and hydrogen. The carbon dioxide is obtained from the atmosphere while the hydrogen is obtained during the electrolysis of water. An intermediate fuel, namely methyl alcohol may be stored for use or upgraded to higher heating value hydrocarbons by a catalytic conversion";
we can react Carbon Dioxide directly with Hydrogen to make, through "methyl alcohol", "gasoline", maybe we could trade them some of our Carbon Dioxide, so that they can make Gasoline, in Florida, out of that Carbon Dioxide, in exchange for some of their Hydrogen; so that we can make, as per the above-noted "United States Patent 3,960,700 - Coal Hydrogenation to Produce Liquids", "liquid hydrocarbons", in Coal Country, out of Coal.
And, we don't know about you, but, we would a whole lot rather, in any case, be importing "synthetic fuel" from Florida, and exporting Coal to Florida, rather than importing any more OPEC oil, after having been able for the past several decades to export to those old boys only more of our dollar bills and more of our young people in uniform.
But, there is, as they say, more to the story.
Bamberger spent a lot of time developing the technology disclosed by our subject, "United States Patent 4,180,555 - Producing Hydrogen from Water Using Cobalt and Barium Compounds"; and, we might in the future touch on some of his preliminary work.
The important thing is, though, that both Bamberger and others built on the foundation laid herein; and, they all developed somewhat different, and more advanced, techniques that not only enable the more efficient generation of Hydrogen, at lower temperatures, but also, in a way related to that seen in our report of:
West Virginia Coal Association | USDOE Recycles CO2 to Methanol with Solar Power | Research & Development; concerning: "United States Patent 6,066,187 - Solar Reduction of CO2; 2000; Government Interests: This invention was made with government support ... (from) the U.S. Department of Energy to The Regents of the University of California. The government has certain rights in the invention. Abstract: The red shift of the absorption spectrum of CO2 with increasing temperature permits the use of sunlight to photolyze CO2 to CO. The product CO may be used to generate H2 by the shift reaction or to synthesize methanol";
developed more evolved, and involved, processes that enable, with the Hydrogen, the transformation of Carbon Dioxide, as recovered from whatever handy source, into even more liquid hydrocarbon fuels - as we will document for you in a number of reports to follow.
