We have lately been studying the work of one USDOE scientist, whom we might have cited once or twice previously, which centers on the efficient electrolytic production of Hydrogen from Water, H2O.
As we've seen in a number of previous reports, such as:
West Virginia Coal Association | US Navy 2008 CO2 to Synfuel | Research & Development; concerning: "United States Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels; 2008; Assignee: The USA, as represented by the Secretary of the Navy; Abstract: A process for producing synthetic hydrocarbons that reacts carbon dioxide, obtained from seawater or air, and hydrogen obtained from water, with a catalyst in a chemical process such as reverse water gas shift combined with Fischer Tropsch synthesis. A system for producing synthetic hydrocarbons, comprising: (a) a unit for recovering carbon dioxide from seawater, air, or a combination thereof; (b) a unit for producing hydrogen from water; and (c) a Fischer Tropsch synthesis unit wherein ... methanol production is combined with Fischer Tropsch synthesis to produce said hydrocarbons from said carbon dioxide and said hydrogen"; and:
West Virginia Coal Association | Standard Oil Converts Coal with Methane and Hydrogen | Research & Development; concerning: "United States Patent 4,326,944 - Rapid Hydropyrolysis of Carbonaceous Solids; 1982; Assignee: Standard Oil Company of Indiana; Abstract: A method is disclosed for recovering liquids and gases by a rapid hydropyrolysis of carbonaceous solids which comprises subjecting the carbonaceous material in a stream of carrier gas to (specified reaction conditions, and) wherein the carbonaceous material is coal (and) wherein the carrier gas is hydrogen";
Hydrogen in its elemental form can be utilized to great good effect in the conversion of both Carbon Dioxide and Coal into liquid and gaseous hydrocarbons.
As indicated in the above-cited "United States Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels", it is feasible on a practical basis to react Hydrogen directly with Carbon Dioxide to form hydrocarbons. However, as we've also seen in other reports, such reactions typically result in the production of more of what are referred to as "oxygenated hydrocarbons", that is, various alcohols, which, though very useful to have, are not in and of themselves direct replacements for conventional liquid hydrocarbon fuels.
Thus, as in the now-generic Fischer-Tropsch synthesis, as seen in:
Fischer–Tropsch process - Wikipedia, the free encyclopedia; "a set of chemical reactions that convert a mixture of carbon monoxide and hydrogen into liquid hydrocarbons";
Carbon Monoxide is most often specified as the preferred reactant for the Hydrogen.
And, as can be learned via:
West Virginia Coal Association | Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development; concerning: "United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes; 1987; Assignee: The Standard Oil Company; Abstract: A process for the electrocatalytic reduction of carbon dioxide comprises immersing a transition metal complex with square planar geometry into an aqueous or nonaqueous solution which has been acidified to a (specified) hydrogen ion concentration ... , adding the carbon dioxide, applying an electrical potential of from about -0.8 volts to about -1.5 volts ... , and reducing the carbon dioxide to carbon monoxide";
we do have some efficient means available to us for making the Carbon Monoxide electrochemically, from water solutions of Carbon Dioxide.
So, the efficient production of Hydrogen, to be available as a reactant for either Carbon Dioxide or Carbon Monoxide, in the synthesis of various hydrocarbons, is of some significant importance; and, as seen, for just one example, in:
USDOE Algae Make Hydrogen for Coal and CO2 Hydrogenation | Research & Development; concerning: "United States Patent 4,442,211 - Method for Producing Hydrogen and Oxygen by Use of Algae; 1984; Inventor: Elias Greenbaum, Oak Ridge, TN; Assignee: The United States of America; Abstract: Efficiency of process for producing H2 by subjecting algae in an aqueous phase to light irradiation is increased by culturing algae which has been bleached during a first period of irradiation in a culture medium in an aerobic atmosphere until it has regained color and then subjecting this algae to a second period of irradiation wherein hydrogen is produced at an enhanced rate. A method of producing H2 and O2 by use of algae and light";
our USDOE has invested some effort into devising efficient means of producing it.
And, one way, another way, to produce Hydrogen is similar to that for producing Carbon Monoxide from Carbon Dioxide as disclosed in the above-cited "United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes"; that is, from Water, H2O, via electrolysis, as in:
Hydrogen from Wind Power | Research & Development; concerning: "United States Patent 7,329,099 - Wind Turbine and Energy Distribution System; 2008; Inventor: Paul Hartman; Abstract: A new design of vertical axis wind turbine is disclosed ... . An apparatus for conversion of a wind energy resource into rotational power ... coupled to electrical generating means (which) is connected to an electrical load (and, which) electrical load comprises at least one electrolysis cell, said at least one electrolysis cell connected to an output stream of hydrogen gas and further connected to an input stream of water".
Further, such electrolyses of Carbon Dioxide and Water can proceed concurrently, in tandem, as has been explained by our USDOE and their contractors in, for just two examples:
Utah 2011 CO2 + H2O = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; 2011; Inventors: Joseph Hartvigsen; Assignee: Ceramatec, Inc.; Abstract: A method is provided for synthesizing synthesis gas from carbon dioxide obtained from atmospheric air or other available carbon dioxide source and water using a sodium-conducting electrochemical cell. Synthesis gas is also produced by the coelectrolysis of carbon dioxide and steam in a solid oxide fuel cell or solid oxide electrolytic cell. The synthesis gas produced may then be further processed and eventually converted into a liquid fuel suitable for transportation or other applications"; and:
Idaho Recycles CO2 | Research & Development; concerning: "Syntrolysis: Simultaneously electrolyzing water and carbon-dioxide into Syngas; Two global energy priorities today are finding environmentally friendly alternatives to fossil fuels, and reducing greenhouse gases like carbon dioxide. Idaho National Laboratory researchers have invented a technology that can do both. INL’s Syngas Generation from Co-Electrolysis uses high-temperature nuclear reactor technology and solid-oxide fuel cell technology to recycle carbon dioxide and water into Syngas, the feedstock for synthetic hydrocarbon fuel production. This breakthrough technology also is called Syntrolysis, which is a patent-pending process that leverages nuclear-powered high-temperature electrolysis at 750-950C in a solid-oxide electrolysis cell to convert water and carbon dioxide into synthesis gas. “Using the well-understood Fischer-Tropsch process, Syngas can subsequently be converted into synthetic hydrocarbon fuels,” said INL nuclear engineer Steve Herring".
However, the above-noted USDOE "Syntrolysis" technology requires a high-temperature, high-energy environment, where both the CO2 and the H2O are in their gaseous forms. The energy and physical plant requirements to accomplish such a process could entail some great deal of expense, although the process does otherwise seem highly efficient.
Herein, we see that the USDOE scientist we mentioned in our initial comments had, some time ago, developed a perhaps somewhat, but only somewhat, "milder" version of the process described above in our citation of "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water"; a version which combines aspects of "United States Patent 7,329,099 - Wind Turbine and Energy Distribution System" and "United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes"; and, which leads to the generation, from Carbon Dioxide mixed with Water, of a blend of Carbon Monoxide and Hydrogen, a "syngas" blend suitable for the catalytic synthesis of hydrocarbons.
Comment follows excerpts from the initial link in this dispatch to:
"United States Patent 4,313,925 - Thermochemical Cyclic System for Decomposing H2O and/or CO2 by Means of Cerium-Titanium-Sodium-Oxygen Compounds
Date: February, 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 begins with the reaction of ceric oxide (CeO2), titanium dioxide (TiO2) and sodium titanate (Na2TiO3) to form sodium cerous titanate (NaCeTi2O6) and oxygen. Sodium cerous titanate (NaCeTi2O6) reacted with sodium carbonate (Na2CO3) in the presence of steam, produces hydrogen. The same reaction, in the absence of steam, produces carbon monoxide. The products, ceric oxide and sodium titanate, obtained in either case, are treated with carbon dioxide and water to produce ceric oxide, titanium dioxide, sodium titanate, and sodium bicarbonate. After dissolving sodium bicarbonate from the mixture in water, the remaining insoluble compounds are used as starting materials for a subsequent cycle. The sodium bicarbonate can be converted to sodium carbonate by heating and returned to the cycle.
(Note, as indicated above, Carbon Dioxide is utilized and consumed in two separate stages of the process, i.e., in the generation of the synthesis gas product and in the regeneration of the "sodium cerous titanate" reagent from the co-product "ceric oxide and sodium titanate"; and, which regenerated "sodium cerous titanate" is recycled back into the process, thus conserving materials and reducing expense. However, some segments of the process, such as the above "sodium bicarbonate can be converted to sodium carbonate by heating", will generate Carbon Dioxide of their own; and, although the Carbon Dioxide is recycled back into the system, it does limit the amount of Carbon Dioxide which can be added from an outside source.)
Claims: A method for producing sodium cerous titanate comprising reacting ceric oxide, titanium dioxide and sodium titanate at a temperature above 900C to cause the formation of sodium cerous titanate and oxygen.
A method for producing hydrogen comprising reacting sodium cerous titanate, sodium carbonate and steam at a temperature above 500C to produce ceric oxide, sodium titanate, carbon dioxide and hydrogen.
(Again, some Carbon Dioxide is generated, and recycled, within the system itself.)
The method ... wherein said steam is provided in the form of a mixture of steam and inert carrier gas, said mixture being preheated to at least 300C.
A cyclic process for the production of hydrogen from water comprising the steps of:
(a) reacting ceric oxide, titanium dioxide and sodium titanate at a temperature above 900C. to cause formation of sodium cerous titanate and oxygen;
(b) reacting thus-produced sodium cerous titanate with steam and one of sodium carbonate and sodium bicarbonate at a temperature above 500C to produce ceric oxide, sodium titanate, carbon dioxide and hydrogen, which is removed from the reaction environment;
(c) reacting sodium titanate produced in step (b) with water and carbon dioxide to produce titanium dioxide and sodium bicarbonate and removing the thus-produced sodium bicarbonate; and
(d) recycling ceric oxide produced in step (b), titanium dioxide produced in step (c) and sodium titanate remaining from step (c) to step (a).
The process .... wherein ceric oxide, titanium dioxide and sodium titanate are heated at 900 -1200C to produce sodium cerous titanate and oxygen.
The process ... wherein sodium cerous titanate and sodium carbonate are reacted at a temperature between 500 and 1000C. with steam preheated to about 300C to produce ceric oxide, sodium titanate, carbon dioxide and hydrogen.
The process ... wherein ceric oxide, titanium dioxide and sodium titanate are heated at 900.-1200C to produce sodium cerous titanate and oxygen and wherein sodium cerous titanate and sodium carbonate are reacted at a temperature between 500C and 1000C with steam preheated to about 300C to produce ceric oxide, sodium titanate, carbon dioxide and hydrogen.
A cyclic process for the production of hydrogen from water comprising the steps of:
(a) reacting cerium oxide, titanium dioxide and sodium titanate at a temperature above 900C to cause formation of sodium cerous titanate and oxygen;
(b) reacting the thus-produced sodium cerium titanate with molten alkali-metal hydroxide to form ceric oxide, an alkali metal titanate, water, and hydrogen, which is removed from the reaction environment;
(c) reacting incompletely sodium titanate produced in step (b) with boiling water to produce sodium hydroxide and titanium dioxide, and removing the thus-produced sodium hydroxide; and
(d) recycling ceric oxide produced in step (b), titanium dioxide produced in step (c) and sodium titanate remaining from step (c) to step (a).
Description: As the prospect of hydrogen utilization becomes increasingly likely, methods for producing hydrogen need to be upgraded and increased. The conventional source of hydrogen has been electrolysis of water. Electrolysis, however, is highly inefficient owing to a maximum efficiency below 40% for electricity production coupled with a maximum efficiency of about 80 percent for electrolysis. Electrolytic production of hydrogen is limited by the overall futility of using one energy source, typically fossil fuels, at the point of electricity production to produce hydrogen at the point of electrolysis. The disadvantages of using irreplaceable fossil fuels are obviously not overcome by such a process.
Chemically feasible processes for the direct conversion of fossil fuels and water to hydrogen are available and overcome many of the inefficiencies and disadvantage of electrolysis.
However, prudence dictates that ... (fossil) fuels (be) conserved for use as chemical intermediates.
Thermochemical processing is therefore a most attractive alternative method for producing hydrogen. By this technique, water is broken down to hydrogen and oxygen in a series of chemical reactions not requiring the use of fossil fuels..
Objects: An object of any thermochemical process is the direct use of heat from an energy producing facility requiring no fossil fuels, e.g., a ...solar source.
It is a further object of this invention to provide a novel cyclic thermochemical process for splitting water into hydrogen and oxygen.
In addition, this invention provides a novel thermochemical route for the production of carbon monoxide.
A further object of this invention is to provide a thermochemical route to hydrogen or carbon monoxide, carried out using reactants and reaction products which are markedly less corrosive than used in previously known processes, which employs abundant and inexpensive materials and which is simpler than known processes because the cyclic system operates efficiently regardless of minor cross contamination and, therefore, does not require complete separation of reactants or products.
These and other objects are accomplished in a three-step process in the first step of which ceric oxide, titanium dioxide and sodium titanate are reacted to produce sodium cerous titanate and oxygen.
Summary: In one aspect, this invention relates to a cyclic process for the production of hydrogen from water comprising the steps of:
(a) reacting ceric oxide, titanium dioxide and sodium titanate at a temperature above 900.degree. C. to cause formation of sodium cerous titanate and oxygen;
(b) reacting thus-produced sodium cerous titanate with steam and one of sodium carbonate and sodium bicarbonate at a temperature above 500C to produce ceric oxide, sodium titanate, carbon dioxide and hydrogen, which is removed from the reaction environment;
(c) reacting sodium titanate produced in step (b) with water and carbon dioxide to produce titanium dioxide and sodium bicarbonate and removing the thus-produced sodium bicarbonate; and
(d) recycling ceric oxide produced in step (b), titanium dioxide produced in step (c) and sodium titanate remaining from step (b) to step (a).
In another aspect, the invention relates to a cyclic process for the production of hydrogen from water comprising the steps of:
(a) reacting cerium oxide, titanium dioxide and sodium titanate at a temperature above 900C to cause formation of sodium cerous titanate and oxygen;
(b) reacting the thus-produced sodium cerium titanate with molten alkali-metal hydroxide to form ceric oxide, an alkali metal titanate, water, and hydrogen, which is removed from the reaction environment;
(c) reacting incompletely sodium titanate produced in step (b) with boiling water to produce sodium hydroxide and titanium dioxide, and removing the thus-produced sodium hydroxide; and
(d) recycling ceric oxide produced in step (b), titanium dioxide produced in step (c) and sodium titanate remaining from step (c) to step (a).
(Note, in the above two steps, the removal of "the thus produced sodium hydroxide". We attempt explanation of its significance in following comments.)
In another aspect, this invention relates to a cyclic process for the production of carbon monoxide comprising the steps of:
(a) reacting ceric oxide, titanium dioxide and sodium titanate at a temperature above 900C to cause formation of sodium cerous titanate and oxygen;
(b) reacting thus-produced sodium cerous titanate with one of sodium carbonate and sodium bicarbonate at a temperature above 900C to produce ceric oxide, sodium titanate, carbon dioxide and carbon monoxide, which is removed from the reaction environment;
(Thus, some, but not all, of the Carbon Dioxide bound in the "sodium carbonate and sodium bicarbonate" is converted into Carbon Monoxide. But, the question is, where do the "sodium carbonate and sodium bicarbonate" come from in the first place? And, we refer you back to the removal of "the thus produced sodium hydroxide" i.e. NaOH, noted above, in conjunction with one of our earlier reports:
West Virginia Coal Association | New York City Reclaims and Recycles Carbon Dioxide | Research & Development; concerning: "US Patent Application 20110011945A1 - System and Method for Removing CO2 from an Atmosphere; 2011; Inventors: Peter Eisenberger, NJ, and Graciela Chichilnisky, NY; Abstract: A system for removing carbon dioxide from an atmosphere to reduce global warming including an air extraction system that collects carbon dioxide from the atmosphere through a medium and removes carbon dioxide from the medium (and) wherein the medium is an NaOH solution".
We note, in passing, that rights to the above US Patent, if and when it issues, will likely be assigned to:
"Global Thermostat, LLC; New York, NY: Global Thermostat's patent-pending technology uses low-cost left over process heat as energy for the capture of CO2 from the atmosphere. It can be installed at new or legacy power plants, cement smelters, refineries, etc. Since energy typically accounts for two-thirds of the total operating cost with other carbon capture technologies, Global Thermostat's solution allows for dramatic cost efficiencies in reducing carbon emissions."
For more info, visit: Global Thermostat.)
(c) reacting incompletely sodium titanate produced in step (b) with water and carbon dioxide to produce titanium dioxide and sodium bicarbonate; and removing the thus-produced sodium bicarbonate; and
(d) recycling ceric oxide produced in step (b), sodium titanate remaining from step (c) and titanium dioxide produced in step (c) to step (a).
In addition, this invention relates to a method for producing sodium cerous titanate comprising reacting ceric oxide, titanium dioxide and sodium titanate at a temperature above 900C to cause the formation of sodium cerous titanate and oxygen.
This invention further relates to a method for producing hydrogen comprising reacting sodium cerous titanate, sodium carbonate and steam at a temperature above 500C to produce ceric oxide, sodium titanate, carbon dioxide and hydrogen and further to a method for producing carbon monoxide comprising heating sodium cerous titanate and sodium carbonate at a temperature above 900C to form carbon monoxide, carbon dioxide, ceric oxide and sodium titanate.
In another aspect, this invention relates to a cyclic process for the production of carbon monoxide comprising the steps of: reacting ceric oxide, titanium dioxide and sodium titanate at a temperature above 900C to cause formation of sodium cerous titanate and oxygen (and) reacting thus-produced sodium cerous titanate with one of sodium carbonate and sodium bicarbonate at a temperature above 900C. to produce ceric oxide, sodium titanate, carbon dioxide and carbon monoxide, which is removed from the reaction environment".
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Again, the system isn't perfect, since some of the Carbon Dioxide brought into the system, bound as "sodium carbonate", or sodium bicarbonate, as might be generated by the process of "US Patent Application 20110011945A1 - System and Method for Removing CO2 from an Atmosphere", as cited above, is regenerated as a co-product with the Carbon Monoxide; and, the CO2 is recycled within the system, as seen, for one example, in the passage: "reacting sodium titanate produced in step (b) with water and carbon dioxide to produce titanium dioxide", which "titanium dioxide" goes on to help form the needed cyclic reagent "sodium cerous titanate".
Since the "carbon monoxide ... is removed from the reaction environment" as one product, we'll assume that material balances remain intact with the subtraction of the Carbon in the "removed" Carbon Monoxide, and allow the importation of more Carbon Dioxide, bound as "sodium carbonate", preferably as the product from an atmospheric CO2 collection device that uses NaOH as the scrubbing medium.
We'll have more on the use of "NaOH", Sodium Hydroxide, as an efficient CO2 collection medium in future reports; and, remind you, that, if you examine our excerpts from the full Disclosure, you'll see that one step specifies "removing the thus-produced sodium hydroxide", presumably for use in a process such as that disclosed in "US Patent Application 20110011945A1", for gathering more Carbon Dioxide.
The process of our subject, "United States Patent 4,313,925 - Thermochemical Cyclic System for Decomposing H2O and/or CO2", is, as you can tell, complex.
But:
The materials it utilizes as reagents, such as "cerous titanate", though exotic-sounding, aren't precious, that is, unacceptably high cost; and, further, they aren't used up to any appreciable extent in the process, acting simply as material transfer agents that "leverage", for want of a better term, the extraction of Hydrogen and Carbon Monoxide from compounds that contain them, thus reducing the energy costs, through a more complicated reaction sequence, of producing what amounts to a hydrocarbon synthesis gas blend of Carbon Monoxide and Hydrogen from raw materials that amount only to Water, H2O, and what could be the effluent, or product, of an efficient device that uses Sodium Hydroxide to scrub Carbon Dioxide from the atmosphere.