United States Patent: 8313634
First, up front, we herein again confirm that Carbon Dioxide, as it arises in only a small way, relative to natural sources of emission, such as volcanoes, from our economically essential use of Coal in the generation of abundant and truly economical electric power, is a valuable raw material resource.
We can reclaim Carbon Dioxide, from whatever convenient source, and then convert that CO2 on a practical basis into a variety of commercially important compounds, including fuel alcohols and hydrocarbons.
In a recent dispatch, now accessible via:
West Virginia Coal Association | Saudi Arabia and Texas CO2 to Hydrocarbon Syngas | Research & Development; we made report of:
"United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture; October 16, 2012; Assignee: Saudi Basic Industries Corporation, Riyadh; Abstract: The invention relates to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, wherein the catalyst substantially consists of chromia/alumina. This process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions. The process can be applied separately, but can also be combined with other processes, for example up-stream with other synthesis processes for making products like aliphatic oxygenates, olefins or aromatics".
As often happens, in a phenomenon we have called to your attention on several occasions, the official United States Government link we included in that dispatch, to the official United States Patent and Trademark electronic file of "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture", no longer functions properly, and now takes you to a different US Patent record entirely.
We'll address that presently; but, we first remind you that we included in that dispatch an additional link to a secondary site's record of "United States Patent 8,288,446"; and, an additional independent link to it in our separate report of:
West Virginia Coal Association | Saudi Arabia Converts Even More CO2 into Hydrocarbon Syngas | Research & Development;
which was actually concerned more with Saudi Arabia's multiple international patent applications for their practical Carbon Dioxide recycling technologies.
Those links to the secondary site records of "United States Patent 8,288,446" still function properly at the time of this writing, and we'll not include more of them here.
Serendipitously, however, again as often seems to be the case with altered US Patent and Trademark Office links, almost as if someone in the USPTO were lending us a hand, the official USPTO link in our original report concerning "US Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture" now takes you to a US Patent record that might, in fact, be even more intriguing, in terms of the potentials for profitably reclaiming Carbon Dioxide and transforming it on a practical basis into needed hydrocarbons.
We remind you of yet another of our earlier reports, from more than a year and a half ago, accessible via:
West Virginia Coal Association | Princeton Recycles CO2 with US Government Support | Research & Development; concerning:
"United States Patent Application 20100187123A1 - Conversion of Carbon Dioxide to Organic Products; Publication Date: July 29, 2010; Inventors: Andrew B. Bocarsly and Emily Barton Cole; Government Interests: This invention was made with United States government support from Natural Science Foundation Grant No. CHE-0606475. The United States Government has certain rights in this invention. The invention relates to various embodiments of an environmentally beneficial method for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in a divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor cathode electrode in another cell compartment that also contains an aqueous solution of an electrolyte and a catalyst of one or more substituted or unsubstituted aromatic amines to produce therein a reduced organic product";
wherein scientists at New Jersey's prestigious Princeton University, whom we've now cited in multiple reports, disclosed, subsequent to research and development funded by the US Government, how Carbon Dioxide could be profitably transformed into, among other things, both Methanol and Ethanol.
And, by way of reminder, we reproduce here an excerpt from that US Patent Application, concerning where the Carbon Dioxide raw material might come from:
"Advantageously, the carbon dioxide used in the embodiments of the invention can be obtained from any sources, e.g., an exhaust stream from fossil-fuel burning power or industrial plants, from geothermal or natural gas wells or the atmosphere itself. Most suitably, however, carbon dioxide is obtained from concentrated point sources of its generation prior to its release into the atmosphere. For example, high concentration carbon dioxide sources are those frequently accompanying natural gas in amounts of 5 to 50%, those from flue gases of fossil fuel (coal, natural gas, oil, etc.) burning power plants, and nearly pure CO2 exhaust of cement factories and from fermenters used for industrial fermentation of ethanol. Certain geothermal steams also contains significant amounts of CO2. In other words, CO2 emissions from varied industries, including geothermal wells, can be captured on-site. Separation of CO2 from such exhausts is well-developed. Thus, the capture and use of existing atmospheric CO2 in accordance with embodiments of the invention allows CO2 to be a renewable and unlimited source of carbon."
Please note appropriate mention of those darlings of our infatuated public press, "natural gas", and of the misguided and shallowly-informed environmental lobby, "fermenters used for industrial fermentation of ethanol", as significant "point sources" of Carbon Dioxide.
As it happens, that US Patent Application has proven successful; and, the official USPTO link in our recent report of:
West Virginia Coal Association | Saudi Arabia and Texas CO2 to Hydrocarbon Syngas | Research & Development; "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture";
now takes you, fortuitously, again as if the dedicated scientific and technical minds at the USPTO were helping us out, to, as excerpted from the initial link in this dispatch, and as issued just yesterday:
"United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products
(Conversion of carbon dioxide to organic products - Princeton University)
Date: November 20, 2012
Inventors: Andrew Bocarsly and Emily Barton Cole, NJ
Assignee: Princeton University, NJ
Abstract: The invention relates to various embodiments of an environmentally beneficial method for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in a divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor cathode electrode in another cell compartment that also contains an aqueous solution of an electrolyte and a catalyst of one or more substituted or unsubstituted aromatic amines to produce therein a reduced organic product.
Government Interests: This invention was made with United States government support from National Science Foundation Grant No. CHE-0616475. The United States Government has certain rights in this invention.
Claims: A method of converting carbon dioxide to provide at least one product selected from the group consisting of glyoxal, isopropanol, ethanol, 2-propanol, acetone, acetaldehyde and mixtures thereof, comprising reducing the carbon dioxide electrochemically in a divided electrochemical cell comprising an anode in one cell compartment and a cathode in another cell compartment, the cathode selected from the group consisting of Gold, Silver, Zinc, Gallium, Mercury, Indium, Cadmium, Titanium, Platinum and hydrogenated Palladium, the cell compartment including the cathode including one or more substituted or unsubstituted aromatic heterocyclic amines, each compartment containing an aqueous solution of an electrolyte, wherein said at least one product selected from the group consisting of glyoxal, isopropanol, ethanol, 2-propanol, acetone, acetaldehyde and mixtures thereof is generated in the electrolyte by reduction of carbon dioxide and the aromatic heterocyclic amine is selected from the group consisting of lutidines and bipyridines, and mixtures thereof.
(Note that we do not need all of the metal "cathode" catalysts specified; but, it seems, only one selected from the identified group.
Note further, and this is important, and it is emphasized deep within the full Disclosure, the method of this invention requires no external source of molecular Hydrogen. All of the needed Hydrogen, to chemically reduce the Carbon Dioxide, and to combine chemically with CO2 in the synthesis of various "organic products", is itself generated within the system from the "aqueous solution".)
The method ... wherein the cathode is selected from the group consisting of Platinum and hydrogenated Palladium.
(The claims go one at some length specifying and describing a variety of organic chemical compounds that can be/are to be utilized, as we take it, as promoters of the needed reactions, in conjunction with the metal catalyst. The full nomenclature of those organic compounds, as stated by Bocarsly and Cole, is beyond our full understanding, as we imagine it would be for the vast majority of our readers. However, our cursory survey of available literature suggests that all of the organic compounds specified are well-known in certain scientific circles; and, that the techniques and technologies for making them are well-established. - JtM)
The method ... which further comprises obtaining the carbon dioxide from an exhaust stream from a fossil fuel burning power or industrial plant, from a source accompanying natural gas ... .
The method ... wherein electrical energy for the electrochemical reduction of carbon dioxide is provided from an energy source based on ... hydroelectric, wind, geothermal or solar power.
Description: In recent years, high levels of atmospheric carbon dioxide (CO2), emitted, for example, from industry, fossil fuel combustion and utilities, have been linked to global climate change. A greenhouse effect attributed to carbon dioxide is indicated as one cause of the warming phenomenon of the earth. Many responsible sources contend that the condition of the earth's atmosphere is such that, to avoid the predicted dire consequences of global warming effects, removal of a portion of the existing, as well as new, quantities of carbon dioxide from the atmosphere is needed.
Various options for carbon dioxide reduction have been proposed. In addition to energy conservation, carbon capture and storage, the process of separating CO2 from emission sources and transporting it to a storage location for long-term (indefinite) isolation, and carbon sequestration, the process of permanently storing CO2 underground, have garnered the most attention to date. However, these technologies face significant challenges and are presently far from being cost effective. In addition, sequestration has raised serious environmental concern, legal and regulatory issues due to the unknown ramifications of permanently storing CO2 underground.
A significant issue with the removal of carbon dioxide from the atmosphere is the very large energy input to overcome the entropic energies associated with isolating and concentrating a diffuse gas. As noted, current strategies for removal of carbon dioxide from the atmosphere are either inefficient, cost prohibitive, or produce toxic by-products such as chlorine. To lower global carbon dioxide levels and reduce new carbon dioxide emissions, it remains critical to develop economically feasible processes to remove vast quantities of carbon dioxide from the atmosphere or gas streams.
In accordance with embodiments of the invention, an electrocatalytic system is provided that allows carbon dioxide to be converted at very modest overpotentials to highly reduced species in aqueous solution. In other words, carbon-carbon and/or carbon-hydrogen bonds are formed in aqueous solution under very mild condition utilizing a minimum of energy. In some embodiments, the required energy input may be generated from an alternative energy source or directly using visible light depending on how the system is implemented.
In embodiments of the invention, the reduction of carbon dioxide is suitably catalyzed by aromatic heterocyclic amines, e.g., pyridinium, imidazole and their substituted derivatives. These simple organic compounds have been found to be effective and stable homogenous electrocatalysts and photoelectrocatalysts for the aqueous multiple electron, multiple proton reduction of carbon dioxide to organic products such as formic acid, formaldehyde, and methanol.
(We are compelled to interrupt here to emphasize a few things. The above "formic acid" product of Carbon Dioxide recycling, as seen in:
West Virginia Coal Association | England Improves Coal Liquid Hydrogenation with Formic Acid | Research & Development; concerning: "United States Patent 4,313,852 - Catalysts; 1982; Assignee: Coal Industry Limited, London; Abstract: A hydrotreating catalyst which is resistant to carbonaceous deposits and is particularly useful for hydrotreating coal-derived liquids, is molybdenum or tungsten disulphide ... . The catalyst can be made by absorbing molybdenum or tungsten trisulphide onto the active carbon support and reducing the trisulphide to the disulphide. Claims: A hydrotreatment catalyst comprising molybdenum or tungsten disulphide ... . (And, a) method of producing (the) catalyst comprising molybdenum or tungsten disulphide (by) absorbing molybdenum or tungsten trisulphide onto an active carbon support ... and reducing the trisulphide to the disulphide. (And) wherein the reduction is effected using ... formic acid (or) sodium formate";
can be employed in, among other things, some processes for the conversion of Coal, or "coal-derived liquids", into hydrocarbons. It has a lot of other intriguing potentials, as well, which we will eventually get around to more fully documenting for you.
The above "formaldehyde" product of Carbon Dioxide recycling can, as seen in:
Urea-formaldehyde - Wikipedia, the free encyclopedia; "Urea-formaldehyde ... is a ... resin or plastic, made from urea and formaldehyde (which) are used in adhesives, finishes, ... and molded objects";
be consumed in the making of certain plastics, wherein the CO2 consumed in the synthesis of the Formaldehyde would be forever, and productively, "sequestered".
And, the above "methanol" product of Carbon Dioxide recycling can, as seen in:
West Virginia Coal Association | Mobil Oil Coal to Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline; 1984;
Assignee: Mobil Oil Corporation; Abstract: A process for producing a wide slate of fuel products from coal is provided by integrating a methanol-to-gasoline conversion process with coal liquefaction and coal gasification. The coal liquefaction comprises contacting the coal with a solvent under supercritical conditions whereby a dense-gas phase solvent extracts from the coal a hydrogen-rich extract which can be upgraded to produce a distillate stream. The remaining coal is gasified under oxidation conditions to produce a synthesis gas which is converted to methanol. The methanol is converted to gasoline by contact with a zeolite catalyst. Solvent for coal extraction is process derived from the upgraded distillate fraction or gasoline fraction of the methanol-to-gasoline conversion";
no matter which of our precious resources, whether, as above, Coal, or, as per the process of our subject herein, "United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products", Carbon Dioxide, we make it from, can be efficiently converted into that essential of modern life, Gasoline.)
It has previously been thought that metal-derived multi-electron transfer was necessary to achieve highly reduced products such as methanol. Surprisingly, the simple aromatic heterocyclic amine molecules in accordance with embodiments of the invention are capable of producing many different chemical species on route to methanol through multiple electron transfers instead of metal-based multi-electron transfer.
The invention thus relates to various embodiments of environmentally beneficial methods for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in an aqueous, electrolyte-supported divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor working cathode electrode in another cell compartment that contains a catalyst of one or more substituted or unsubstituted aromatic heterocyclic amines to produce a reduced organic product. CO2 is continuously bubbled through the cathode electrolyte solution to saturate the solution.
The catalyst for conversion of carbon dioxide electrochemically or photoelectrochemically may be selected from any substituted or unsubstituted aromatic heterocyclic amine. Suitable amines are heterocycles which are 5- or 6-member rings with at least one ring nitrogen. For example, pyridine, imidazole and their substituted derivatives have been found to be especially suitable as catalysts for either the electrochemical reduction or the photoelectrochemical reduction. It is also envisioned the other aromatic amine, e.g., quinolines, are also effective electrocatalysts.
Embodiments of the present invention relate to the simple, efficient, and economical conversion of carbon dioxide to reduced organic products, such as methanol, formic acid and formaldehyde.
It has been previously known that carbon dioxide can be photochemically or electrochemically reduced to formic acid with formaldehyde and methanol being formed in only smaller amounts. Catalytic hydrogenation of carbon dioxide using heterogeneous catalysts is also known to provide methanol together with water as well as formic acid and formaldehyde.
(The) use of processes for converting carbon dioxide to reduced organic products in accordance with embodiments of the invention has the potential to lead to a significant reduction of carbon dioxide, a major greenhouse gas, in the atmosphere, thus to mitigation of global warming. Moreover, the present invention advantageously produces methanol and related products without the need of adding extra reactants, such as a hydrogen source.
The resultant product mixture requires little in the way of further treatment.
In ... accordance with embodiments of the invention, process steps are carried out at temperatures of 10C to 50C. and pressures of 1 to 10 atmospheres unless otherwise specified.
(Note that high temperatures and high pressures, with their attendant investment of energy and expense, are not required.)
It has now been found that the use of electrochemical or photoelectrochemical reduction of carbon dioxide (CO2), tailored with certain electrocatalysts, produces methanol and related products in a high yield of about 60 to about 100%, based on the amount of CO2, suitably about 75 to 90%, and more suitably about 85 to 95%. At an electric potential of about -0.09 to -0.5 V with respect to a standard calomel electrode (SCE), methanol can be produced with good faradaic efficiency at the cathode.
(Note in the above, that, as in our report of:
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; 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";
the choice of proper catalysts can reduce the amount of electricity needed for the electrochemical reduction of CO2 to the point where the needed juice could, we would think, be fairly easily supplied by Princeton's specified "hydroelectric, wind, geothermal or solar power"; i.e, any "alternative energy source".)
(The chemical) reduction of CO2 (as fully disclosed herein) can suitably yield formaldehyde, formic acid, glyoxal, methanol, isopropanol, or ethanol, depending on the particular aromatic heterocyclic amine used as the catalyst. In other words, in accordance with the invention, the products of the reduction of CO2 are substitution-sensitive. As such, the products can be selectively produced.
The effective electrochemical/photoelectrochemical reduction of carbon dioxide disclosed herein provides new methods of producing methanol and other related products in an improved, efficient, and environmentally beneficial way, while mitigating CO2-caused climate change (e.g., global warming).
Moreover, the methanol product of reduction of carbon dioxide can be advantageously used as:
(1) a convenient energy storage medium, which allows convenient and safe storage and handling;
(2) a readily transported and dispensed fuel, including for methanol fuel cells; and:
(3) a feedstock for synthetic hydrocarbons and their products currently obtained from oil and gas resources, including polymers, biopolymers and even proteins ... .
Advantageously, the carbon dioxide used in the embodiments of the invention can be obtained from any sources, e.g., an exhaust stream from fossil-fuel burning power or industrial plants, from geothermal or natural gas wells or the atmosphere itself. Most suitably, however, carbon dioxide is obtained from concentrated point sources of its generation prior to its release into the atmosphere. For example, high concentration carbon dioxide sources are those frequently accompanying natural gas in amounts of 5 to 50%, those from flue gases of fossil fuel (coal, natural gas, oil, etc.) burning power plants, and nearly pure CO2 exhaust of cement factories and from fermenters used for industrial fermentation of ethanol. Certain geothermal steams also contains significant amounts of CO2. In other words, CO2 emissions from varied industries, including geothermal wells, can be captured on-site. Separation of CO2 from such exhausts is well-developed. Thus, the capture and use of existing atmospheric CO2 in accordance with embodiments of the invention allows CO2 to be a renewable and unlimited source of carbon."
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Once again, as we've documented, for one more example, in:
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; September 13, 2011; Assignee: The United States of America as represented by the Secretary of the Navy";
Carbon Dioxide, as it is emitted from our economically vital use of Coal in the generation of abundant and truly affordable electricity - - just as it is emitted in large quantities in the making of cement and clean, green Corn ethanol - - is a valuable raw material resource.
And, that is a fact, that, as seen in:
Obama spokesman: “We would never propose a carbon tax” - Business, Government Legal News from throughout WV; concerning the report: "Obama spokesman: 'We would never propose a carbon tax'; November 15, 2012; By Taylor Kuykendall; Directly taxing emission of carbon dioxide to thwart its effect on climate has been much talked about post-election, but a spokesman for the president said it's off the table. By implementing a tax on carbon dioxide emissions, many believed significant reductions of greenhouse gas emissions could be achieved absent the complicated system of cap-and-trade that failed Congressional muster in 2010. The coal industry likely stands to suffer the most from any sort of tax on carbon dioxide emissions. At a press conference Wednesday, President Barack Obama emphasized a need to address climate change, but White House Press Secretary Jay Carney said that something would not be a "carbon tax." "We would never propose a carbon tax and have no intention of proposing one," Carney said in a press briefing. "The point the president was making is that our focus right now is the same as the American people's focus, which is on the need to extend economic growth, expand job creation";
might well be known and recognized by someone who, loudly, and we think falsely, maligned by the Coal Country press, has, through actions such as those seen, for just two examples, in our reports of:
West Virginia Coal Association | Obama White House Blocked EPA Coal Ash 'Hazardous' Label | Research & Development; and
West Virginia Coal Association | Obama White House Says China Coal-to-Liquids = US Jobs | Research & Development;
belied the suspect and worn-out jingoism of our popular press, and proven himself an ally of the Coal industry, just as, as when he stood as a co-sponsor of:
Coal-to-Liquid Fuel Promotion Act of 2007 (2007; 110th Congress S. 155) - GovTrack.us; "Senate Bill S.155, entitled the "Coal-To-Liquid Fuel Promotion Act of 2007", "A bill to promote coal-to-liquid fuel activities", was introduced to the 110th Congress on January 4, 2007. Among it's formal sponsors were Robert Byrd and Barack Obama";
he stood not just as an ally of Coal, but as an ally of one of the great champions of US Coal Country: the late, great Senator Robert Byrd, in an action that should have won headlines throughout US Coal Country, but, as far as we have so far been able to determine, went entirely unacknowledged.
We wonder if the facts confirmed herein by Princeton University and, through their issuance, just yesterday, of our subject, "United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products", by unbiased technical experts in the employ of our United States Government, that, "under very mild conditions" and "utilizing a minimum of energy", we can "selectively" convert Carbon Dioxide, as reclaimed from whatever convenient source, into such seemingly-desirable things as "ethanol", "methanol", "formic acid", and "formaldehyde", will ever, in the public press of US Coal Country, be openly acknowledged.
It should be. It ain't politics, but hard science. Hard science that, if openly acknowledged and implemented, could mean more hard cash going into the pockets of US citizens and less hard cash flowing into the oversized treasuries of OPEC and Big Oil; and, less hard cash flowing out of US Coal Country in the form of Cap and Trade taxes, which might fall on us when a successor to Obama, who "would never propose a carbon tax", ultimately takes up residence in the White House, and, like some of Obama's predecessors, might see such a "carbon tax" as a popular way in other parts of the nation to raise revenues and thereby reduce a national debt that won't do anything but keep growing - - growing, as long as we feel obliged to pay fealty to OPEC through our imports of foreign oil and pay, as well, through our Department of Defense, to keep Persian Gulf shipping lanes open and the Middle Eastern deserts peaceful enough to pump oil.
We have some choices we can make here; but, we can't make the choices unless we know that we do, in fact, have choices available to us to be made.
It is a bitter, bitter shame that we don't, apparently, among our Coal Country public press, have any true champions for Coal - - champions even close to what the late Senator Robert Byrd and now-President Barack Obama proved, and have proven, themselves to be.
