West Virginia Coal Association | US Navy Awarded September, 2011, CO2 Recycling Patent | Research & Development
With our profound regrets for clutter and duplication, we are compelled herein to repeat a previous disptatch.
As too often happens with United States Patent and Trademark Office official links to documents in the their electronic library, the USPTO link we included in our headlined report has proven to be not durable, and now links up, almost serendipitously, with another US Patent issued for Carbon Dioxide recycling technology.
We have previously addressed the CO2-recycling technology demonstrated in that separate US Patent; and, since it's again now linked to one of our reports, might address it again.
However, lest anyone think that the technology we addressed in that original report, concerning the United States Navy and the fact that they darned-well know how to convert Carbon Dioxide into liquid hydrocarbon fuels, is specious or imaginary, we reproduce our original report below, following two independent site links to that US Patent, as in:
Synthesis of hydrocarbons via catalytic reduction of CO2 - The United States of America as represented by the Secretary of the; and:
Patent US8017658 - Synthesis of hydrocarbons via catalytic reduction of CO2 - Google Patents.
Those links function properly at this time, as does the current, following link to the USPTO's official file:
United States Patent: 8017658.
Further, we have downloaded and saved a copy of the document itself.
That said, again with our profound regrets for the rework and the repetition, following is the text of our original report, concerning the plain fact that Carbon Dioxide can be efficiently harvested from the environment itself, and, on a practical basis, then be converted into liquid hydrocarbon fuels; as follows:
"We have previously reported on the accomplishments of our US Defense establishment in the development of technologies which would enable us to reclaim Carbon Dioxide, whether from point sources of emission or from the environment itself, and then to convert that reclaimed Carbon Dioxide into liquid hydrocarbon fuels.
Achievements were made in that arena by components of our military very nearly half a century ago, as we documented, for just one instance, in:
US Air Force 1965 CO2 to Fuel Conversion | Research & Development; concerning: "Catalytic Reduction of Carbon Dioxide to Methane and Water; Foreword: This report summarizes the work accomplished under contract AF 3"(615)-1210, for research on catalytic reduction of carbon dioxide to methane and water. The effort was initiated (in) 1964 (and) was monitored by (the) Environmental Control Branch (FDFE), Air Force Flight Dynamics Laboratory, Research and Technology Division, Wright-Patterson Air Force Base, Ohio."
Efforts continued along similar paths over the following decades, with Defense Department contractors being enlisted to help, as witness, for just one example, our report of:
CO2 to Synfuel Production Ship | Research & Development; concerning: "US Patent 4,568,522 - Synfuel Production Ship; 1986; Grumman Aerospace Corporation; 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."
Those efforts continued, and we saw that the United States Navy itself had successfully achieved the conversion of CO2, reclaimed from the environment, into liquid hydrocarbon fuels, in our report of:
US Navy and Columbia University Recycle Atmospheric CO2 | Research & Development; which includes, among other things, information concerning: "United States Patent 7,420,004 - Process and System for Producing Synthetic Liquid Hydrocarbon Fuels; 2008; 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 (can be) produced by ... any (energy) source that is fossil fuel-free, such as wind or wave energy."
And, we learned that our US Navy has, since then, continued to refine their Carbon Dioxide recycling technology to an even greater degree, as documented in our report, from one year ago, of:
US Navy Seeks CO2 Recycling Patent | Research & Development; concerning: "United States Patent Application 2008/0051478A1 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2; 2008; Inventors: Nick Tran, Dennis Hardy, et. al., DC and VA; Assignee: The Government of the US, as represented by the Secretary of the Navy; Abstract: A method of: introducing hydrogen and a feed gas containing at least 50 volume % carbon dioxide into a reactor containing Fischer-Tropsch catalyst; and heating the hydrogen and carbon dioxide to a temperature of at least 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 for feeding into the reaction vessel; a carbon dioxide delivery system for delivering a feed gas containing at least 50 volume % carbon dioxide feeding into the reaction vessel; and a trap for collecting hydrocarbons generated in the reaction vessel".
Herein, we see that our United States Navy's US Patent Application 2008/0051478A1, as above, was successful, and, as excerpted from the initial link in this dispatch, has resulted in the recent award of:
""United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2
Date: September 13, 2011
Inventors:Nick Tran, Dennis Hardy, et. al., DC 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 % 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 % carbon dioxide feeding into the reaction vessel; and a trap for collecting hydrocarbons generated in the reaction vessel.
Claims: A method comprising: introducing hydrogen and a feed gas containing at least 50 % 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; wherein the catalyst is a kieselguhr supported catalyst comprising cobalt, potassium, thorium, and magnesium.
The method wherein the feed gas contains no more than 10 ppm carbon monoxide.
The method ... wherein the feed gas contains no more than 10 ppm methanol.
(In other words, we don't need any "carbon monoxide" or "methanol", at all, to start with, just CO2.)
The method ... wherein the hydrogen and carbon dioxide are introduced into the reactor as gases.
The method ... comprising: collecting the hydrocarbons in a trap; and cooling the hydrocarbons to liquid or solid form.
The method ,,, comprising: extracting the hydrogen from water.
(Which can be done efficiently, as witness, for just one instance, our report of:
More NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,051,005 - Photolytic Production of Hydrogen; 1977; United Technologies Corporation; Government Interests: The invention described herein was made in the course of a contract with the NASA; Abstract: Hydrogen and oxygen are produced from water in a process involving the photo-dissociation of molecular bromine with radiant energy ... wherein the source of radiation is sunlight".)
The method ... further comprising: extracting the carbon dioxide from air.
(See, again, our report of:
US Navy and Columbia University Recycle Atmospheric CO2 | Research & Development; which contains separate information concerning: "US Patent 7,833,328 - Scrubber for Capturing Carbon Dioxide from Air; 2010; Columbia University; A scrubber apparatus for capturing carbon dioxide from open air".),
The method ... further comprising: extracting the carbon dioxide from combustion of the hydrocarbons.
(See, for instance, our report of:
2011 Efficient Extraction of Flue Gas CO2 | Research & Development; concerning: "United States Patent 7,927, 572 - Purifying Carbon Dioxide and Producing Acid; 2011; Praxair Technology, Inc.; Carbon dioxide is purified by processes employing NOx-rich sulfuric acid that can be formed by removal of SO2 from the carbon dioxide (and) wherein said gaseous feed stream of carbon dioxide is formed by combustion.)
The method ... wherein the feed gas contains at least 90 % carbon dioxide.
Field and Description: The invention is generally related to hydrocarbon synthesis.
There are several well-established processes for direct hydrogenation of gases such as CO or CO2 to produce hydrocarbon fuels.
One of the most successful was developed in Germany in the 1920s by Franz Fischer and Hans Tropsch. In 1938, early German plants produced 591,000 tons per year ... of oil and gasoline using the Fischer-Tropsch process, which reacts carbon monoxide and hydrogen with a catalyst to produce liquid hydrocarbons.
They used fossil fuels (i.e., Coal.) to produce the CO, CO2, and H2 used.
Additionally, well-known methods have been developed to produce methanol from carbon dioxide and hydrogen.
Methanol can also be used as a feedstock to produce traditional automotive gasoline.
The problem with these methods is that the (flash points of methanol and gasoline are too low, and, due to regualtions) these methods cannot be used at sea, since the International Maritime Organization and the U.S. Navy require a minimum 60 C. flash point for all bulk flammable liquids on ships.
(Don't miss the point of the foregoing discussion: Our US Navy herein isn't concerning itself with making either Methanol or Gasoline from Carbon Dioxide. First, they want a less-volatile fuel. Second, we already know how to convert Carbon Dioxide into Methanol, and, through Methanol, into Gasoline.)
Summary: The invention comprises a method comprising: introducing hydrogen and a feed gas containing at least 50 % 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.
The invention further comprises an apparatus comprising: a reaction vessel for containing a Fischer-Tropsch catalyst, capable of heating gases contained therein 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 % carbon dioxide feeding into the reaction vessel; and a trap for collecting hydrocarbons generated in the reaction vessel.
Current synfuel technology uses coal ... .
The present invention can use CO2 and H2 as feedstocks to produce high Molecular Weight (MW) hydrocarbons, which can be turned into synfuels.
In addition, some of the high MW hydrocarbon products can be high value compounds (normally difficult to synthesize). The method may produce at least 4 generic types of relatively high MW compounds: wax, waxy aromatics, waxy condensed aromatic ring compounds, and alcohols.
The method involves the reaction of hydrogen and carbon dioxide using a Fischer-Tropsch catalyst to produce hydrocarbons.
Fischer-Tropsch catalysts are known in the art (and, such) catalyst include, but are not limited to, platinum group metals, ruthenium, rhodium, cobalt, nickel, iron, molybdenum, tungsten, palladium, platinum, iridium, rhenium, osmium, and any such metals on a support such as alumina, kieselguhr, zeolite, silica, and titanium dioxide. One example catalyst is a kieselguhr supported cobalt-based catalyst (KCBC) containing kieselguhr, cobalt, magnesium, thorium, and optionally potassium.
(The exotic-sounding "kieselguhr", by the way, is an inexpensive, porous clay mineral. Think of an old, traditional, "meerschaum" tobacco pipe, and you'll be close to the mark.)
The hydrogen and carbon dioxide can be introduced into the reactor in gaseous form. The carbon dioxide feed gas contains at least 50, 75, 90, or 99 % carbon dioxide.
Any means of delivering the gas may be used, including but not limited to, from a gas cylinder or as the product of another process. For example, the hydrogen may be extracted from water or seawater by electrolysis. The carbon dioxide may be extracted from the ambient air or from sea water. When the hydrocarbons that are made from the process are subsequently combusted, carbon dioxide is produced, which may be used as the feedstock carbon dioxide. Hydrogen and carbon dioxide that are not directly derived from fossil fuels may be used. As used herein, carbon dioxide in the ambient atmosphere or environment is not considered to be directly derived from fossil fuels.
(Although, of course, some of it, in truth, indirectly, is.)
The reaction may take place with little to no carbon monoxide or methanol in the feed gas. The carbon monoxide concentration may be no more than about 10 ppm, 1 ppm, 0.5 ppm, or 0.2 ppm. Commercially available carbon dioxide tanks typically contain less than 0.2 ppm carbon monoxide. The concentration of methanol may be no more than about 10 ppm or 1 ppm.
The reaction may occur in a single vessel in one step.
(It is, thus, with "a single vessel" and "one step", a simple process.)
The hydrogen and carbon dioxide are heated to at least about 190 C. The heating may occur in the reactor or before the gas is introduced into the reactor. The temperature used may be at least partially dependent on the gas pressure. Generally, a higher gas pressure may require a lower temperature. There is no upper limit on the pressure, as long as the hydrogen and carbon dioxide remain in gas form, and may, for example, be as high as thousands of psi. One suitable reaction condition is a temperature of about 190 C to about 220 C with hydrogen gas pressure of about 250 to about 300 psi (at room temperature). The hydrogen gas pressure may be about 2.8 to about 3.2, including 3, times the carbon dioxide gas pressure to have about a 3:1 stoichiometric ratio.
(Those pressures and temperatures are within the ranges easily, and commonly, employed by modern chemical industry. This is not a high-tech, futuristic nuclear fusion reactor we're talking about here.)
The hydrocarbons can be collected in a trap and cooled to liquid or solid form. The product may be a waxy substance containing high molecular weight hydrocarbons. The hydrocarbons may contain hydroxyl, carbonyl, and carboxyl groups. The waxy material can be refined to produce hydrocarbon fuels.
The hydrocarbons may be produced and refined at the point of use, for example, at sea."
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Or, how about at the point of Carbon Dioxide production, "for example", along the Ohio River?
Make no mistake:
This is clear presentation of the fact that we know, without doubt, how to, efficiently, convert Carbon Dioxide into liquid hydrocarbon fuels.
It is technology that has been developed by genuine patriots employed by our United States Government, and certified to be viable and practical by other patriots in the employ of our United States Government.""
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We are deeply uncomfortable with the tedium, and the uncertainty, such replication and repetition, as in the above, might present for our readers.
Issues such as "phantom", insubstantial links to official US Government documents serve to cloud the issues we have been attempting to address, i.e.: that Coal, and CO2-recycling Biomass, can be efficiently converted, together, into liquid hydrocarbon fuels, into anything at all that we now import, as it were, at gunpoint, from OPEC; that Carbon Dioxide can be efficiently harvested and, as herein, converted into the same sorts of things; and, that Coal Ash can serve as more economical, better-performing and more environmentally-friendly substitute for the traditional raw materials in the making of Portland-type Cement and Concrete, and Concrete aggregates.
And, we regret the need we feel to, on a continuing basis, police the issue in a way and in a venue that will, because especially of unreliable US Government technical support services, make all of the concepts we have been attempting to define and establish in terms of their indisputable, concrete reality seem doubtful and questionable.
It is far, far past time the mainstream Coal Country press and Coal Country news outlets behooved themselves to get off their dead cans and do what, long, long ago now they should've done; what they should, all along, have been doing:
Anchoring and establishing once and for all, for their customers, the Coal Country public, the Truths, that:
Coal can be efficiently converted into liquid hydrocarbon fuels, into anything we are now selling out our nation and our children's future to OPEC in order to keep ourselves supplied with here and now.
Coal Ash is a valuable mineral commodity that can supplant virgin raw materials in the making of cement and concrete, in processes that result in lower emissions of Carbon Dioxide and, overall, in the consumption of less energy; and, result in cement and concrete products that are demonstrably better in terms of physical properties and other parameters of performance than those made from the traditional raw materials.
And:
Carbon Dioxide, according to multiple branches of our own United States Government, is a valuable raw material resource.
As confirmed herein by the United States Navy, via their Disclosure of "US Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2", we can reclaim Carbon Dioxide, even from the environment itself, and, on a practical basis, convert, recycle, that CO2 into conventional liquid hydrocarbon fuels
