United States Patent Application: 0130206605
We remind you that, as seen, for three examples, in our reports of:
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; Inventors: Dennis Hardy and Timothy Coffey, VA; 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. The hydrogen is produced by nuclear reactor electricity, nuclear waste heat conversion, ocean thermal energy conversion, or any other source that is fossil fuel-free, such as wind or wave energy. The process can be either land based or sea based. Claims: 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";
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; 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 volume percent 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 in the reactor. An apparatus having: a reaction vessel for containing a Fischer-Tropsch catalyst, capable of heating gases to at least about 190 C; a hydrogen delivery system feeding into the reaction vessel; a carbon dioxide delivery system for delivering a feed gas containing at least 50 volume percent carbon dioxide feeding into the reaction vessel; and a trap for collecting hydrocarbons generated in the reaction vessel";
(Patent US8017658 - Synthesis of hydrocarbons via catalytic reduction of CO2 - Google Patents
West Virginia Coal Association | US Navy May 7, 2013, CO2 to Liquid Hydrocarbon Fuels | Research & Development; concerning: "United States Patent 8,435,457 - Synthesis of Hydrocarbons Via Catalytic Reduction of CO2; 2013; Inventors: Nick Tran, Dennis Hardy, Samuel Lambrakos, John Michopoulos; DC, MD and VA; 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 vol % 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 in the reactor. An apparatus having: a reaction vessel for containing a Fischer-Tropsch catalyst, capable of heating gases to at least about 190 C; a hydrogen delivery system feeding into the reaction vessel; a carbon dioxide delivery system for delivering a feed gas containing at least 50 vol % carbon dioxide feeding into the reaction vessel; and a trap for collecting hydrocarbons generated in the reaction vessel";
(Patent US8435457 - Synthesis of hydrocarbons via catalytic reduction of CO2 - Google Patents
our United States Navy has, over the course of years, established a substantial body of technology irrefutably and thoroughly confirming an immensely important fact:
Carbon Dioxide, as it arises in only a small way, relative to some natural sources of emission, such as the Earth's inexorable processes of planetary volcanism, from our economically essential use of Coal in the generation of truly abundant, truly reliable, and truly affordable electric power, can be and should be seen and treated as a valuable raw material resource.
We can reclaim Carbon Dioxide from the environment around us, and, then, in some cases using environmental energy to drive the processes, convert that Carbon Dioxide, along with Hydrogen, even Hydrogen derived from abundant and constantly renewing ocean water, into liquid hydrocarbon fuels; into anything we now make from the crude petroleum imported at great cost to our nation and to our people from the alien, foreign, and often inimical, nations of OPEC.
Please note that, in our above citations of those past reports, we have appended additional links to secondary site records of the US Navy's United States Patents concerning their CO2-recycling technologies. As too often happens, the official United States Patent and Trademark Office links to the USPTO's electronic files of those documents, in those prior reports, have proven unreliable. We assure you: The documents, and the CO2-recycling technologies disclosed by them, are quite real; and, our intent in including the additional reference links is to be as thorough and as meticulous as possible in our documentation of facts which many might view with almost insurmountable incredulity.
We also note, that, in at least one of our prior reports, the one concerning "US Patent 8,435,457 - Synthesis of Hydrocarbons Via Catalytic Reduction of CO2" specifically, we made an error in the transcription of patent numbers in our excerpts, which sadly might have contributed to confusion on the part of those interested enough to search the available electronic records themselves.
In any case, the same problem with web links and electronic files is true, albeit for different reasons, of the document we make report of herein, another of the US Navy's Carbon Dioxide utilization technologies.
As seen in our earlier report, from July 23, 2012, of:
West Virginia Coal Association | US Navy Recovers More CO2 for Hydrocarbon Synthesis | Research & Development; concerning: "United States Patent Application 20110281959 - Extraction of Carbon Dioxide and Hydrogen from Seawater and Hydrocarbon Production Therefrom; Publication Date: November, 2011;
Inventors: Feice DiMascio, Dennis Hardy, et. al., CT, MD, VA and PA; Assignee: The Government of the United States of America as Represented by the Secretary of the Navy; Abstract: Apparatus for seawater acidification including an ion exchange, cathode and anode electrode compartments and cation-permeable membranes that separate the electrode compartments from the ion exchange compartment. Means is provided for feeding seawater through the ion exchange compartment and for feeding a dissociable liquid media through the anode and cathode electrode compartments. A cathode is located in the cathode electrode compartment and an anode is located in the anode electrode compartment and a means for application of current to the cathode and anode is provided. A method for the acidification of seawater by subjecting the seawater to an ion exchange reaction to exchange H+ ions for Na+ ions. Carbon dioxide may be extracted from the acidified seawater. Optionally, the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide. The carbon dioxide and hydrogen may be used to produce hydrocarbons";
the US Navy had developed, and published report of, a more complete and integrated technology intended to enable the coordinated extraction of both Carbon Dioxide and Hydrogen from abundant ocean water and their subsequent transformation into hydrocarbons.
None of the links we included with that report now function. But, as it happens, "United States Patent Application 20110281959 - Extraction of Carbon Dioxide and Hydrogen from Seawater and Hydrocarbon Production Therefrom", remains quite real, quite viable, and has been proceeding through the US Patent application process. And, apparently with advisement from technical experts in the employ of the United States Patent and Trademark Office, our US Navy scientists have revised "Application 20110281959" slightly, which is the likely reason for all the original electronic links to it in various databases now failing to function, and have now republished it, as excerpted from the initial link in this dispatch, as:
"United States Patent Application 20130206605 - Extraction of Carbon Dioxide and Hydrogen from Seawater and Hydrocarbon Production Therefrom
Date: August 15, 2013
Inventors: Felice DiMascio, Dennis Hardy, et. al., CT, MD, VA and PA
Assignee: The Government of the United States of America as represented by the Secretary of the Navy
Abstract: Apparatus for seawater acidification including an ion exchange, cathode and anode electrode compartments and cation-permeable membranes that separate the electrode compartments from the ion exchange compartment. Means is provided for feeding seawater through the ion exchange compartment and for feeding a dissociable liquid media through the anode and cathode electrode compartments. A cathode is located in the cathode electrode compartment and an anode is located in the anode electrode compartment and a means for application of current to the cathode and anode is provided. A method for the acidification of seawater by subjecting the seawater to an ion exchange reaction to exchange H+ ions for Na+ ions. Carbon dioxide may be extracted from the acidified seawater.
Optionally, the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide. The carbon dioxide and hydrogen may be used to produce hydrocarbons.
Claims: A method for treatment of seawater comprising the step of subjecting the seawater to an ion exchange reaction to exchange H+ ions for Na+ ions in the seawater (and) wherein the conditions are sufficient to lower a pH of the seawater to less than about 4.5.
(In truth, a pH of "less than about 4.5" is getting fairly acidic. As operated at a scale on board a ship, for fueling the fleet, any discharge of water that acidic into the ocean would be absolutely negligible in it's effect. However, if a land-based facility operating the process were to be constructed on shore, along the coast, to operate the process on a scale meaningful for the supply of liquid hydrocarbon fuel for land transportation purposes, then provision would absolutely have to be made for the neutralization of the pH levels. Although the buffering capability of the ocean is vast, and in the grand scheme such discharge would ultimately be inconsequential, there is no doubt there would be harmful localized harmful effects on the oceanic environment in the area where the acidified seawater would be discharged. The problem can be resolved, as seen further on, since "Na+ ions" are being made available through displacement by "H+ ions".)
The method ... wherein a current density resulting from applied current is from about 5 to about 200 (milliamps per square centimeter).
(For a large scale operation, that could actually add up to a lot of juice. But, therein lies a huge opportunity for the deployment of various wind, solar and hydro facilities to generate electricity from site-appropriate environmental energy to power the process. Although sites where enough environmental energy, or in the case of hydro, potential environmental energy, is present in enough volume to generate electricity in amounts meaningful enough to warrant construction of facilities for the supply of electricity to the "grid" are relatively few and far between, and often in geographic locations that make their exploitation impractical, it might, as a practical matter, be feasible to construct a smaller-scale solar, wind or hydro facility in the available space to supply the specific needs of Carbon Dioxide recycling facility operating the Navy's processes.)
The method ... wherein sufficient current is applied in the ion exchange reaction to generate excess hydrogen (and) further comprising the step of separating carbon dioxide from acidified seawater obtained from the ion exchange reaction (and) further comprising the step of separating hydrogen from a liquid ion exchange media obtained from the ion exchange reaction.
The method ... further comprising the step of producing hydrocarbons from the carbon dioxide obtained in the carbon dioxide separation step and the hydrogen obtained from the liquid ion exchange media.
The method ... wherein the carbon dioxide is separated from the acidified seawater by vacuum stripping (and) wherein the hydrogen is separated from the liquid ion exchange media by vacuum stripping.
An electrolytic process for producing carbon dioxide and hydrogen gas from seawater comprising: feeding a liquid anolyte into an anode compartment to generate hydrogen ions; feeding a liquid catholyte substantially free of hardness ions into a cathode compartment, wherein the central compartment is separated from the anode and cathode compartments by cation exchange membranes; feeding seawater into the central compartment; acidifying the seawater by exchanging the hydrogen ions for sodium ions therein to produce an acidified seawater effluent from the central compartment; reacting the sodium ions with hydroxyl ions in the cathode compartment to produce an effluent comprising sodium hydroxide and hydrogen gas; reacting carbonate and bicarbonate ions in the acidified seawater with the hydrogen ions to produce carbon dioxide; and removing the carbon dioxide from the acidified seawater and removing the hydrogen gas from the cathode compartment effluent.
(Note, in the above, the co-production of "sodium hydroxide", NaOH, along with the "hydrogen gas". We submit that such a strong base as "NaOH" would be ideal for neutralizing the "acidified seawater"; with the chemical products of such a neutralization being almost utterly innocuous, virtually harmless. Though not really detailed or well-explained, the Navy does stipulate such a neutralization in the full Claims.)
The process ... wherein the seawater fed to the central compartment is filtered to less than 20 microns (and)comprising periodically reversing flow of current to the cathode and anode.
(There are specifications for the process of "reversing flow of current"; and, our take on it is that it's being done to remove deposits of salts, etc., on the electrodes which could ultimately impair performance. )
The process ... wherein removing the carbon dioxide from the acidified seawater and/or removing the hydrogen gas from the cathode compartment effluent comprises applying a vacuum to extract the carbon dioxide and/or the hydrogen gas (and) wherein vacuum applied is -30 in Hg and greater.
(And, in the above, we, here, encounter a problem. The "-30 in Hg" is, as we understand it, a perfect vacuum; and is, in theory, not achievable, much less one that is "greater". However, a pressure differential of "-30 in Hg and greater" could be achieved by generating vacuum on the one side and somehow, perhaps by heating, generating gas pressure on the other. That, we think, is something that needs clarified. It might be an ideal specification for complete scavenging of the CO2 and H2; which isn't, really, we would think, needed.)
The process ... further comprising producing aqueous hydrocarbons from the carbon dioxide and hydrogen gas.
The process ... further comprising the extracting carbon dioxide and hydrogen gas from the seawater at a molar ratio of 1 to 2 (or) 1 to 3.
A process for treating seawater in an electrolytic reactor to produce carbon dioxide gas and hydrogen gas comprising: electrolytically generating hydrogen ions from water in an anode compartment; exchanging sodium ions in the seawater with the hydrogen ions in an amount effective to reduce a pH of the seawater to less than 6.5, wherein exchanging the sodium ions in the seawater with the hydrogen ions forms carbon dioxide gas; electrolytically generating hydroxyl ions and hydrogen gas from water in a cathode compartment; and forming sodium hydroxide from the hydroxyl ions and the sodium ions.
Background and Field: The present invention relates to methods and apparatus for extracting carbon dioxide and hydrogen from seawater and to processes for hydrocarbon production including the carbon dioxide extraction method.
Technologies currently exist to synthesize hydrocarbon fuel on land, given sufficient primary energy resources such as coal.
CO2 as a carbon feedstock could be catalytically reacted with hydrogen to form diesel and/or jet fuel. (As per extended included references.)
The hydrogen could be produced through commercial off the shelf conventional electrolysis equipment, and the electrical energy for this process would be derived through ... Ocean Thermal Energy Conversion (OTEC).
(We've reported on the use of "OTEC", "Ocean Thermal Energy Conversion", to drive processes of carbon conversion and hydrocarbon synthesis previously, as in:
West Virginia Coal Association | US Navy Coal + H2O = Low Cost Methanol | Research & Development; concerning: "United States :Patent 4,476,249 - Low Cost Method for Producing Methanol; 1984; Assignee: The Johns Hopkins University, Baltimore; The Government has rights in this invention pursuant to Contract N00024-78-C5384 awarded by the Department of the Navy. Abstract: Method for producing low cost methanol. A source of carbon is provided to an OTEC plant or plantship which is processed to produce carbon monoxide which is reacted with hydrogen to produce methanol. The oxygen and hydrogen are obtained from the electrolysis of water with the required energy supplied by ocean thermal energy conversion";
where in the "source of carbon" was suggested to be Coal. As a supplement, we'll make separate report on the Navy's more recent, more advanced development of "OTEC" technology in the near future.)
This synthetic fuel production process could provide an alternative energy source to fossil fuels.Practical, efficient, and economical methods of extracting large quantities of CO2 from seawater must be developed before a sea-based synthetic fuel process that combines hydrogen ... with CO2 to make jet fuel can be envisioned.
(This process is specific to recovering CO2 from seawater. We won't include references to past reports, but, we're getting pretty good at extracting it from the atmosphere and from flue gas for hydrocarbon synthesis purposes, as well.)
Summary: In a first aspect, the present invention relates to an apparatus for seawater acidification. The seawater acidification apparatus includes an ion exchange compartment, a cathode electrode compartment, an anode electrode compartment and cation-permeable membranes, which separate the cathode and anode electrode compartments from the ion exchange compartment. The apparatus includes a means for feeding seawater through the ion exchange compartment and means for feeding a liquid media capable of dissociating to provide acidic ions through the anode and cathode electrode compartments. The device also includes a cathode located in the cathode electrode compartment, an anode located in the anode electrode compartment and a means for application of current to each of the cathode and anode to create the driving force for the ion exchange process.
In a second aspect, the present invention relates to a method for the acidification of seawater. In this method, seawater is subjected to an ion exchange reaction to exchange H+ ions for Na+ ions to thereby acidify the seawater.
In a third aspect, the present invention relates to a method for extracting carbon dioxide from seawater. In the method, seawater is subjected to an ion exchange reaction to acidify the seawater to a pH of 6.5 or below by exchange of H+ ions for Na+ ions in the seawater. Once the seawater has been acidified, carbon dioxide is extracted as bound carbon dioxide in the form of bicarbonate, or the acidified seawater is degassed to obtain gaseous carbon dioxide. Optionally, the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide.
(Note that, in addition to high-vacuum degassing, the CO2 can also be extracted "in the form of bicarbonate". We don't know when we'll get to it, but, that has implications for other CO2-utilization technologies developed by others which we will be addressing in future reports.)
In a fourth aspect, the present invention relates to a method for the production of hydrocarbons from seawater. In the method, seawater is subjected to an ion exchange reaction to acidify the seawater to a pH of 6.5 or below by exchange of H+ ions for Na+ ions in the seawater. Once the seawater has been acidified, the acidified seawater is degassed to obtain gaseous carbon dioxide. The carbon dioxide obtained by degassing is fed to a reactor with hydrogen to produce hydrocarbons. Optionally, the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide and the hydrogen produced by the ion exchange reaction can be used as a feed stream to the hydrocarbon production step."
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There is, actually, even more on the way from the Navy regarding such Carbon Dioxide and Hydrogen extraction technologies, so that the CO2 and H2 can be used for "hydrocarbon production".
We'll be addressing those, and the use of Ocean Thermal Energy Conversion, as noted further above, in reports to follow eventually.
In the meantime, keep in mind that, as seen in our report of:
West Virginia Coal Association | US Navy Announces $3/Gallon Jet Fuel from CO2 | Research & Development; concerning the US Naval Research Laboratory news release: ""Fueling the Fleet, Navy Looks to the Seas; September 24, 2012; Refueling U.S. Navy vessels, at sea and underway, is a costly endeavor in terms of logistics, ...and threats to national security and sailors at sea. ... The U.S. Naval Research Laboratory (NRL) is developing the chemistry for producing jet fuel from renewable resources in theater. The process envisioned would catalytically convert CO2 and H2 directly to liquid hydrocarbon fuel used as JP-5. Scientists at the U.S. Naval Research Laboratory (NRL) are developing a process to extract carbon dioxide (CO2) and produce hydrogen gas (H2) from seawater, subsequently catalytically converting the CO2 and H2 into jet fuel by a gas-to-liquids process. (Initial) studies predict that jet fuel from seawater would cost in the range of $3 to $6 per gallon to produce";
the Navy projects that we might be able to produce liquid hydrocarbon fuels, using environmental energy to drive the processes, from the accused environmental pollutant, Carbon Dioxide, at a cost as low as three bucks a gallon.
Have you filled up your car lately? Don't know about you, but, in our neck of the woods, gasoline's been running at a shade more than three and a half bucks a gallon - - the bulk of which, keep in mind, is headed to OPEC to buy more toe rings for the harem girls and more missiles for the sheiks.