United States Patent Application: 0140262792

An article currently appearing as a headline post in many of the Coal-friendly social media web sites, as published originally by the Detroit News, is: 

The war on coal heats up;"The War On Coal Heats Up".

The article says, in part:

"The EPA has developed final rules that set stringent standards for emissions of pollutants from coal-fired power plants. Carbon dioxide is included as a pollutant under the assumption that man-made carbon dioxide is contributing to global warming, that global warming is a bad thing, and that these regulations can have a noticeable effect".

At least one reader has added commentary in the social media to the effect that all the whining and wrangling over Carbon Dioxide emissions from our economically essential Coal-fired generators of genuinely abundant and truly affordable electric power is counter-productive nonsense. That so, since Carbon Dioxide can be seen and treated as a valuable raw material source of Carbon for use and consumption in industrial processes which can synthesize virtually anything, any hydrocarbon fuel or polymer raw material, we now squander our wealth and debase our national integrity to continue buying from those bastions of peace, liberty and democracy that comprise the Organization of the Petroleum Exporting Countries.

As we've documented many times, our own United States Government knows that comment to be true.

And, herein, we submit even further confirmation that our US Government is so well-aware of the raw material value of CO2 that they continue to fund the development of technology for it's productive utilization. 

The University of Delaware, in work funded at least in part by the United States Government, is establishing a complete technology, what might be considered to be a form of "artificial photosynthesis", for the productive recycling of Carbon Dioxide, as recovered from whatever handy source, and the synthesis, from that Carbon Dioxide, of hydrocarbon fuels and chemicals.

We  first remind you of one of our prior reports about one component that work, as accessible via:

USDOE and Delaware Sunshine Extracts Hydrogen from Water | Research & Development | News; concerning: "United States Patent Application 20130175180 - Devices and Methods for Increasing Solar Hydrogen Conversion Efficiency in Photovoltaic Electrolysis; 2013; Inventors: Daniel Esposito, et. al., MD and DE; Assignee: University of Delaware, Newark; Abstract: Devices and methods for photovoltaic electrolysis are disclosed. A device comprises a photovoltaic cell element and an electrolysis compartment. The photovoltaic cell element is configured to convert a portion of solar energy into electrical energy and to pass another portion of the solar energy. The electrolysis compartment includes an aqueous electrolyte positioned to receive the other portion of the solar energy and electrodes electrically connected to receive the electrical energy produced by the photovoltaic cell element. A method comprises receiving solar energy with a photovoltaic cell element, converting a portion of the solar energy into electrical energy, passing another portion of the solar energy through the photovoltaic cell element, receiving with an aqueous electrolyte the other portion of the solar energy, transmitting the electrical energy generated by the photovoltaic cell element to a pair of electrodes, and electrolyzing the aqueous electrolyte with the pair of electrodes. Government Interests: This invention was made with Government support ... by the Department of Energy. The Government may have certain rights in this invention.  A device (and, a) method for photovoltaic electrolysis comprising: receiving solar energy with a photovoltaic cell element; converting a portion of the received solar energy into electrical energy with the photovoltaic cell element; passing another portion of the received solar energy through the photovoltaic cell element; receiving with an aqueous electrolyte the other portion of the solar energy passing through the photovoltaic cell element; transmitting the electrical energy generated by the photovoltaic cell element to a pair of electrodes; and electrolyzing the aqueous electrolyte with the pair of electrodes. This invention relates generally to electrolysis, and more particularly to devices and methods for increasing solar hydrogen conversion efficiency in photovoltaic electrolysis. Photovoltaic (PV) electrolysis allows the generation of hydrogen gas (H2) and oxygen gas (O2) from water using solar energy";

wherein simple and freely-available sunlight can power the extraction of elemental, molecular Hydrogen from the abundant water, H2O, molecule.

Such elemental Hydrogen is reactive enough, that, as seen for one instance in our report of:

USDOE 2012 Coal Power Plant CO2 to Gasoline | Research & Development | News; concerning: "United States Patent 8,226,909 - Systems Including Catalysts in Porous Zeolite Materials Within a Reactor for Use In Synthesizing Hydrocarbons; 2012; Inventors: Harry Rollins, et. al., Idaho; Assignee: Battelle Energy Alliance, LLC, Idaho Falls (USDOE Idaho National Laboratory); Abstract: Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide. ... Government Interests: This invention was made with government support under Contract No. DE-AC07-05ID14517 awarded by the United States Department of Energy. The government has certain rights in the invention. Claims: A system for synthesizing hydrocarbon molecules having two or more carbon atoms from hydrogen and at least one of carbon monoxide and carbon dioxide";

it can enable the synthesis of "Hydrocarbons" directly from Carbon Dioxide. However, in such reactions, the Hydrogen actually first reduces the Carbon Dioxide to Carbon Monoxide and water, H2O, then more Hydrogen reacts with the produced Carbon Monoxide to form both liquid and gaseous hydrocarbons and "oxygenated" hydrocarbons, i.e., alcohols such as "methanol".

And, as seen for just one more recent example in our report of: 

Bayer Improves Fischer-Tropsch Hydrocarbon Synthesis | Research & Development | News; concerning: "United States Patent 8,557,880 - Multi-stage Adiabatic Method for Performing the Fischer-Tropsch Synthesis; 2013; Inventors: Ralph Schellen, et. al., Germany and Texas; Assignee: Bayer Intellectual Property GmbH, Germany; Abstract: The present invention relates to a multistage adiabatic process for performing the Fischer-Tropsch synthesis at low temperatures ... . Claims: Process for preparing liquid hydrocarbons from the process gases carbon monoxide and hydrogen, comprising a Fischer-Tropsch synthesis";

the original and well-known "Fischer-Tropsch synthesis", first developed to enable the conversion of Coal, through an initial gasification, into hydrocarbon fuels, calls for such a blend of "carbon monoxide and hydrogen" in order to minimize and economize Hydrogen consumption, and, to preferentially form more  "liquid hydrocarbons" as opposed to alcohols.

To that end, we learn herein that the University of Delaware, to complement the Hydrogen extracted by solar photo-catalytic processes, as disclosed in their above-cited: "US Patent Application 20130175180 - Devices and Methods for Increasing Solar Hydrogen Conversion Efficiency in Photovoltaic Electrolysis"; have developed an efficient technology for the conversion of Carbon Dioxide, again as collected from whatever convenient source, into Carbon Monoxide.

Comment follows, and is inserted within, excerpts from the initial link in this dispatch to:

"United States Patent Application 20140262792 - System and Process for Electrochemical Conversion of Carbon Dioxide to Carbon Monoxide

SYSTEM AND PROCESS FOR ELECTROCHEMICAL CONVERSION OF CARBON DIOXIDE TO CARBON MONOXIDE - Patent application

SYSTEM AND PROCESS FOR ELECTROCHEMICAL CONVERSION OF CARBON DIOXIDE TO CARBON MONOXIDE - University of Delaware

Date: September 18, 2014

Inventors: Joel Rosenthal, et. al., Delaware

Assignee: University of Delaware, Newark

(We have previously cited the work of UD Professor Joel Rosenthal, and his colleagues. Sadly, our personal insufficiencies prevent us at this time from citing those past reports for you. He is not, we believe, the same Joel Rosenthal who, as seen for one example in our report of:

Chevron 1982 Clean Liquid Hydrocarbons | Research & Development | News; concerning: "United States Patent 4,350,582 - Two-Stage Coal Liquefaction Process with Process-Derived Solvent; 1982; Inventor: Joel Rosenthal, et. al., CA; Assignee: Chevron Research Company, San Francisco; Abstract: Disclosed is a two-stage process for the production of clean liquid hydrocarbons from coal";

developed an array of technologies that enable the efficient conversion of Coal into liquid hydrocarbons for the Chevron Oil Corporation.

More about Dr. Rosenthal and the University of Delaware's work in chemical energy conversion can be leaned via:  .

Chemist Joel Rosenthal awarded research grant in renewable energy conversion; "'Chemist Joel Rosenthal awarded research grant in renewable energy conversion'. April 8, 2014; Joel Rosenthal, assistant professor of chemistry and biochemistry at the University of Delaware, has received a highly competitive Faculty Early Career Development Award from the National Science Foundation (NSF) to support his research in renewable energy and molecular energy conversion. Rosenthal has won widespread attention recently for his work seeking new catalyst platforms that use electricity generated from solar energy to convert carbon dioxide into synthetic liquid fuels for powering cars, homes and businesses. When that type of conversion is successful, carbon dioxide ... can provide a feedstock for the production of synthetic petroleum, offering a potential route to the replacement of fossil fuels"; and:

Selective Conversion of CO2 to CO with High Efficiency Using an Inexpensive Bismuth-Based Electrocatalyst - Journal of the Ame; "Selective Conversion of CO2 to CO with High Efficiency Using an Inexpensive Bismuth-Based Electrocatalyst"; John L. DiMeglio and Joel Rosenthal; Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States; Journal of the American Chemical Society; 2013; Copyright 2013".

The above "Selective Conversion of CO2 to CO with High Efficiency" is an exposition of the technology being fully and formally disclosed herein.)

Abstract: The invention provides a system and a process that allow for the selective electrochemical conversion of carbon dioxide to carbon monoxide with high energy efficiency, using a cathode comprised of bismuth in combination with an anode such as an anode comprised of platinum. The electrolysis system may be comprised of a single or two compartment cell and may employ an organic electrolyte or an ionic liquid electrolyte. The invention permits the storage of solar, wind or conventional electric energy by converting carbon dioxide to carbon monoxide and liquid fuels.

(Note, that, as seen for a few examples in:

USDOE Carbon Monoxide + H2O = Alcohol | Research & Development | News; concerning: "United States Patent 4,656,152 - Catalyst for Producing Lower Alcohols; 1987; Inventor: Jerome Rathke, et. al., Illinois; Assignee: The United States of America, as represented by the Secretary of the USDOE; Abstract: A process and system for the production of the lower alcohols such as methanol, ethanol and propanol involves the reaction of carbon monoxide and water in the presence of a lead salt and an alkali metal formate catalyst combination. The lead salt is present as solid particles such as lead titanate, lead molybdate, lead vanadate, lead zirconate, lead tantalate and lead silicates coated or in slurry within molten alkali metal formate. The reactants, carbon monoxide and steam are provided in gas form at relatively low pressures below 100 atmospheres and at temperatures of 200-400C. The resulted lower alcohols can be separated into boiling point fractions and recovered from the excess reactants by distillation. The United States Government has rights in this invention pursuant to Contract No. W-31-109-ENG-38 between the U.S. Department of Energy and Argonne National Laboratory. Claims: A catalyst combination for the reaction of carbon monoxide and water to produce lower alcohols"; and:

Standard Oil Carbon Monoxide + Water = Gasoline | Research & Development | News; concerning: "United States Patent 4,559,363 - Process for Reacting Carbon Monoxide and Water; 1985; Inventors: Jeffrey Miller and Albert Hensley (Standard Oil Company); Abstract: A process for reacting carbon monoxide and water in the presence of a cadmium-containing catalyst is disclosed. Claims:  A method for the production of hydrocarbons by reacting carbon monoxide and water... . ...This invention relates generally to the reaction between carbon monoxide and water, and more particularly concerns such reaction in the presence of a cadmium-containing catalyst (and, it) is a general object of the present invention to provide a method for the direct production of gasoline"; and:

Pittsburgh 1951 Carbon Monoxide + Water = Hydrocarbons | Research & Development | News; concerning: "United States Patent 2,579,663 - Process of Synthesizing Hydrocarbons; Date: December 25, 1951; Inventor: William Gilbert and Charles Montgomery, PA; Assignee: Gulf Research and Development Company, Pittsburgh; Abstract: This invention relates to a process for synthesizing hydrocarbons; more particularly the invention relates to a process for synthesizing normally liquid hydrocarbons from carbon monoxide and steam. ... We have now discovered that carbon monoxide and steam can be reacted so as to produce among the products of the reaction an important yield of normally liquid hydrocarbons; i.e., hydrocarbons that are liquid at atmospheric temperature and pressure conditions";

it has been well-established that, once we have Carbon Monoxide, as efficiently extracted as herein by the University of Delaware from Carbon Dioxide, that Carbon Monoxide can be reacted with nothing more than plain old water, H2O, perhaps in the form of "steam", and be converted in those reactions into "alcohols" and "liquid hydrocarbons", including, even, "gasoline". And, those processes would be in addition to the above-noted "Fischer-Tropsch", and related, technologies, wherein the Carbon Monoxide is reacted with Hydrogen and thereby made to form, as in Bayer Corporation's above-cited "US Patent 8,557,880 - Multi-stage Adiabatic Method for Performing the Fischer-Tropsch Synthesis;" other "liquid hydrocarbons")

Government Interests: Federal Funding: This invention was made with government support under Grant No. P20-RR017716 awarded by the National Institutes of Health (NIH). The government has certain rights in the invention.

Claims:An electrolytic system for conversion of carbon dioxide to carbon monoxide, the system comprising: an electrode comprised of bismuth and a source of electrical current in electrical communication with the electrode (and) wherein the electrode comprised of bismuth is a cathode (and) wherein the system further comprises an anode and an electrolyte in fluid communication with at least one of the cathode comprised of bismuth or the anode (and)wherein the cathode is in fluid communication with a first electrolyte, the anode is in fluid communication with a second electrolyte, and the first electrolyte and the second electrolyte are the same as or different from each other (and) wherein the electrolyte is an ionic liquid or an organic electrolyte.

The electrolytic system ... wherein the electrolyte is an ionic liquid and the ionic liquid comprises at least one of borate ions, phosphate ions, imidazolium ions, pyridinium ions, pyrrolidinium ions, ammonium ions, phosphonium ions, halides and combinations thereof (and) wherein the electrolyte is an organic electrolyte and the organic electrolyte comprises at least one of acetonitrile, dimethylformamide, dimethyl sulfoxide, a carbonate, and combinations thereof.

The electrolytic system ... wherein the anode is comprised of platinum.

(The "platinum" electrode would be expensive, of course, for a large-scale industrial application of the technology. But, serving as an electrode, it wouldn't be used up or consumed to any appreciable extent in the process. The other chemical compounds named in our excerpts, along with others we're not reproducing, sound complex and exotic, but they are well-known to chemists. And, derived as they are from common elements, as in "borate" and "phosphate", it isn't stuff we would have to have the Mars Rover bring back to Earth for us. It is all well-known, well-established chemistry. It's the combination of the different facets in a process that efficiently converts Carbon Dioxide into Carbon Monoxide that's unique.)

A method for electrochemically converting carbon dioxide to carbon monoxide, wherein the method comprises electrolyzing carbon dioxide in an electrolytic system comprising an electrode comprised of bismuth and a source of electrical current in electrical communication with the electrode (and) further comprising continuously streaming carbon dioxide into the electrolytic system.

(We remind you here of another, similar electrolytic Carbon Dioxide-to-Carbon Monoxide process, as seen in our earlier report of:

Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development | News; concerning:"United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes; 1987; Assignee: The Standard Oil Company, Cleveland; 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". - - -

Although the materials of which the catalytic electrodes are made, and the composition of the electrolytic solutions, are different, the processes of our subject, the University of Delaware's "US Patent Application 20140262792 - System and Process for Electrochemical Conversion of Carbon Dioxide to Carbon Monoxide", and of Standard Oil's above "US Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes", are closely similar in that the energy, the amount of electric current, required by both to extract the desired and desirable Carbon Monoxide from Carbon Dioxide is quite low, and could easily be supplied by alternative sources, such as, as the University of Delaware does specify further on, "wind or solar".

We suspect that :"United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes" is cited by the full documentation accompanying our subject, and will be specified as precedent art if and when any patent issues from the University of Delaware's application.)

The method ... wherein the electrode comprised of bismuth is a cathode and the electrolytic system further comprises an anode and an electrolyte in fluid communication with at least one of the cathode comprised of bismuth or the anode.

(The metal, "bismuth", isn't uncommon or expensive, either. If you've ever reached for the "Pepto-Bismol"(r), aka "pink bismuth" after overindulging at the annual family barbecue, you've actually drunk some.)

The method ... wherein the cathode is in fluid communication with a first electrolyte, the anode is in fluid communication with a second electrolyte, and the first electrolyte and the second electrolyte are the same as or different from each other (and) wherein the cathode is a conducting bismuth or bismuth film cathode and the anode is a platinized anode or a metal oxide anode.

A method of making an electrode comprising electrodepositing a bismuth containing material onto a surface of an inert electrode substrate from either an aqueous, organic or mixed aqueous/organic solution (and) further comprising reducing a solution comprising a precursor to the bismuth containing material and wherein the inert electrode substrate is a carbon or metal-based electrode.

Background and Field: The present invention pertains to systems and processes useful for the electrochemical conversion of carbon dioxide to carbon monoxide.

Storage of solar and other sources of renewable electricity may be enabled by the endothermic production of chemical fuels such as H2 or reduced carbon-containing compounds via the electrochemical reduction of H2O or CO2, respectively.

In particular, the renewable production of liquid fuels provides a clear route to energy supply and distribution and addresses energy needs associated with transportation, which account for more than 20% of US energy demand.

Moreover, liquid fuels are compatible with existing infrastructure for energy supply and distribution. The societal importance and economic value of liquid fuel resources clearly highlights the need for new platforms that enable the sustainable generation of liquid fuels from CO2, and distinguishes CO2 activation and reduction chemistry as a critical area of focus in the fields of renewable energy storage and molecular energy conversion.

An attractive strategy for the synthesis of carbon-based fuels using renewable energy is the marriage of a robust electrocatalyst for CO2 reduction with a photoelectrochemical (PEC) device or a conventional electrolyzer powered by a renewable source of electrical current.

Several CO2 reduction products can be targeted ... . For instance, the direct electrochemical reduction of CO2 to methane or methanol ...  are attractive energy storing reactions.

(With regards to the above statement about electrochemically converting CO2 into substitute natural gas Methane and fuel alcohol Methanol, such technology has been known and available to us, although no one has seen fit to openly and publicly tell us so, for quite some time. See, for example, our reports of:

Chicago Recycles CO2 to Methane | Research & Development | News; concerning: "United States Patent 4,609,440 - Electrochemical Synthesis of Methane; 1986; Assignee: Gas Research Institute, Chicago; Abstract: A method is described for electrochemically reducing carbon dioxide to form methane by electrolyzing an aqueous solution containing carbon dioxide utilizing a cathode which comprises ruthenium. If desired, solar energy can be utilized to provide the potential for the electrolyzing. In such an instance, solar energy is, in essence, stored as chemical energy which can later be recovered from the methane"; and:

USDOE 1976 Atmospheric CO2 to Methanol | Research & Development | News; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Assignee: The USA as represented by the USDOE; Abstract: A method and system for synthesizing methanol from the CO2 in air using electric power. ... In accordance with a preferred embodiment of this invention, a solution of KOH is employed to absorb CO2 from air forming an aqueous solution of K2CO3, the solution is then electrolyzed to produce CH3OH (i.e., Methanol) and reform KOH in solution, the CH3OH is then removed, and make-up water is then added prior to repeating the aforementioned steps. ... By the process described above, it is seen that any source of electrical power may be employed, such as coal-fired power plants. However, from an environmental point of view ... solar energy generated power, would be preferred";)

In addition to being useful for the industrial production of methanol ... and some plastics, ... (a) CO/H2 (Carbon Monoxide/Hydrogen)  mixture (synthesis gas) can be used to generate synthetic petroleum and liquid fuels using existing Fischer-Tropsch (FT) methods for direct integration into existing energy storage and distribution networks.

Carbon monoxide is a valuable commodity chemical that is required for the production of many other products, including plastics (and) is the principal feedstock for the industrial Fischer-Tropsch process, which allows for the large-scale production of synthetic petroleum.

Carbon dioxide is also a waste product from conventional power plants. Collection and sequestration of carbon dioxide is commonplace. The ability to convert this waste product to a commodity chemical such as carbon monoxide can offset the cost of sequestration and is of interest to current power producers. Moreover, an attractive strategy for storage of renewable energy resources such as solar or wind is electrochemical fuel synthesis from carbon dioxide.

(It) would be advantageous to develop technology which bridges this gap by allowing electricity from a photovoltaic assembly, wind turbine, etc. to be used to drive fuel production.

Another desirable development would be technology that provides the ability to generate carbon monoxide directly from carbon dioxide on a small scale. Carbon monoxide is required for commodity chemical synthesis, which includes some pharmaceuticals and other species that require carbonylation and hydroformylation chemistry. Since carbon monoxide is an expensive and toxic feedstock, the ability to generate small quantities of this chemical on demand allows it to be prepared as needed as opposed to relying on large stockpiles of carbon monoxide produced using conventional methods. This strategy would also reduce costs associated with safety and carbon monoxide use.

Summary: The present invention will permit the production of carbon monoxide, which is a valuable commodity chemical and fuel precursor, from atmospheric carbon dioxide, flue gas from a power plant and/or other CO2 streams. Since this energy storing process is driven electrochemically, the invention allows carbon monoxide production to be driven using conventional electric and/or renewable energy resources such as wind or solar. Taken together, this invention will permit storage of solar, wind or conventional electric by converting carbon dioxide to carbon monoxide and liquid fuels."

---------------------------

Although the University of Delaware focuses on the value of Carbon Monoxide - - as can be efficiently extracted from Carbon Dioxide in their process of "United States Patent Application 20140262792 - System and Process for Electrochemical Conversion of Carbon Dioxide to Carbon Monoxide" via, for example, "wind or solar""renewable energy resources" - - as a raw material for synthesizing substitute petroleum "liquid fuels", as perhaps via the "existing Fischer-Tropsch (FT) methods", it is important to emphasize that, as they state, "Carbon monoxide is (also) a valuable commodity chemical that is required for the production of many other products, including plastics"; and, in which "plastics", the Carbon Dioxide consumed in the manufacture of the Carbon Monoxide would be forever, and quite productively, "sequestered".

An example of such technology was revealed in our report of:

Carbon Dioxide Recycled in the Manufacture of Plastics | Research & Development | News; concerning, in part: "United States Patent Application 20040141901 - Process for the Desulfurization of CO Gas; 2004; Correspondence (and presumed Assignee): Bayer Polymers, LLC, Pittsburgh, PA; Abstract: The present invention relates to a process for the preparation of carbon monoxide gas (CO gas) that is free of sulfur compounds to the greatest possible extent, to a process for the desulfurization of a CO gas containing sulfur, and to the use of that gas in chemical syntheses, for example for the synthesis of phosgene from carbon monoxide and chlorine".

Although "phosgene" is most commonly known and thought of as an extremely hazardous "mustard gas", and in point of fact it is, it is also an immensely-valuable and widely-used intermediate chemical in the synthesis of a wide array of high-volume and high-performance plastics and polymers.

And, again, in sum: As once again demonstrated by research and development work funded with our tax dollars, and supervised by our United States Government, and conducted by impeccable scientists at an established and credible institution of higher learning, Carbon Dioxide is a valuable raw material resource.

Carbon Dioxide - -, in processes which need so little energy to drive them that they can be powered by one form or another of environmentally-derived energy, such as the low-level and intermittent electricity that can be generated by "solar" or "wind" installations - - can be converted directly into Carbon Monoxide.

Carbon Monoxide, as so efficiently derived from Carbon Dioxide, can then be used in known and currently-operated industrial processes for the further, productive synthesis of plastics and polymers, and, as the University of Delaware herein specifies, "synthetic petroleum".


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