United States Patent Application: 0110114501

We've now made quite a number of reports documenting the development of an efficient technology for the recycling of Carbon Dioxide, as recovered from whatever source, and it's conversion into synthetic hydrocarbons, by a team of scientists associated with New Jersey's Princeton University.

A few of those reports have included:

Princeton Recycles CO2 with US Government Support | Research & Development; concerning: "US Patent Application 20100187123A1 - Conversion of Carbon Dioxide to Organic Products; 2010; Inventors: Andrew B. Bocarsly and Emily Barton Cole, NJ; 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. A method of converting of carbon dioxide to provide at least one product ... (and) where the at least one product is methanol, isopropanol, formic acid, formaldehyde, glyoxal or ethanol"; and:

 

 

Princeton Scientists Convert More CO2 to Methanol and Ethanol | Research & Development; concerning: "United States Patent Application 20110114502 - Reducing Carbon Dioxide to Products; 2011; Inventors: Emily Barton Cole (and) Andrew Bocarsly, et. al.; A method for reducing carbon dioxide to one or more products is disclosed ... wherein said products ... comprise one or more of acetaldehyde, acetone, carbon, carbon monoxide, carbonates, ethanol, ethylene, formaldehyde, formic acid, glyoxal, glyoxylic acid, graphite, isopropanol, methane, methanol, (etc.)."

As we noted and documented in those, and other, reports concerning those New Jersey-developed Carbon Dioxide recycling developments, the above Bocarsly and Cole are, or were, employed by Princeton University, where the foundational CO2 recycling technologies were first developed; but, that they, and their named co-inventors, were now associated with a new company, "Liquid Light", who will be, we presume, the official assignee of rights when US Patents issue from the above applications.

However, Princeton University will likely share in those rights, and continue to be a part of the process, since, as can be learned from New Jersey's 12th District US Congressman, Rush Holt, via:

Holt, High-Tech Entrepreneurs Talk Job Creation in South Brunswick; wherein it's reported, that: "U.S. Rep. Rush Holt ... visited South Brunswick technology start-up Liquid Light, a small business spun off from Princeton University, to announce a federal grant and meet with the entrepreneurs behind several small high-tech firms. Holt announced that Liquid Light has just received $149,691 in federal support for its technology that converts carbon dioxide – an atmospheric pollutant and greenhouse gas – into butanol, a clean, alternative fuel. “What’s more,” Holt said, “their process is powered by sunlight: an unlimited source of energy that we’ll never have to import from the Middle East”;

"Liquid Light" is some sort of enterprise "spin off" from Princeton University.

In any case, as we read the above-cited United States Patent Applications, "20110114502 - Reducing Carbon Dioxide to Products" and "20100187123A1 - Conversion of Carbon Dioxide to Organic Products", it seems to us that some collection, concentration and purification of Carbon Dioxide is needed before the CO2 can be converted, through the processes of those inventions, into such interesting things as "ethanol, ethylene, ... methane (and) methanol", and, we see herein that Princeton University and Liquid Light have that base covered, as well.

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

"United States Patent Application 20110114501 - Purification of Carbon Dioxide from a Mixture of Gases

Date: May, 2011

Inventors: Kyle Teamey, DC; Emily Cole, Narayanappa Sivasankar, and Andrew Bocarsly, NJ

(As we've noted previously, the ultimate assignee of patent rights is not named in early publications of United States Patent Applications. We assume it will be the Princeton University "spin off", Liquid Light, LLC.)

Abstract: A method for purification of carbon dioxide from a mixture of gases is disclosed. The method generally includes steps (A) and (B). Step (A) may bubble the gases into a solution of an electrolyte and a catalyst in an electrochemical cell. The electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode generally reduces the carbon dioxide into one or more compounds. The anode may oxidize at least one of the compounds into the carbon dioxide. Step (B) may separate the carbon dioxide from the solution.

Claims: A method for purification of carbon dioxide from a mixture of gases, comprising the steps of: (A) bubbling said gases into a solution of an electrolyte and a catalyst in an electrochemical cell, wherein (i) said electrochemical cell comprises an anode in a first cell compartment and a cathode in a second cell compartment, (ii) said cathode reducing said carbon dioxide into one or more compounds and (iii) said anode oxidizing at least one of said compounds into said carbon dioxide; and (B) separating said carbon dioxide from said solution. 

The method ... wherein an energy consumed by said purifying of said carbon dioxide is less than 500,000 watt hours per ton of carbon dioxide. 

The method ... wherein said purification consumes approximately no additional water after said solution has been established in said electrochemical cell.

(What we are attempting to emphasize via the excerpts immediately above is that this is a relatively energy efficient means of extracting and separating purified Carbon Dioxide, from a mix of gases which could, in theory, comprise an industrial exhaust gas, for further processing. One way to translate it, we're told, hopefully accurately, is that we would need "less than" the power equivalent of burning 5,000 hundred-watt light bulbs for an hour to process each ton of CO2.  That still sounds like a lot to us; but, we have no way of translating that into what it might mean in "real" terms of power generation, perhaps, and preferentially, from a non-carbon source. However, the scenario does get better, as they further explain.)

The method ... wherein said compounds comprise one or more of oxalate, oxalate salts, organic acids, oxalic acid, glyoxylic acid and glyoxal. 

A method for purification of carbon dioxide from a mixture of gases, comprising the steps of: (A) bubbling said gases into a solution of an electrolyte in an electrochemical cell, wherein said electrochemical cell comprises an anode in a first cell compartment and a cathode in a second cell compartment; (B) reducing said carbon dioxide into oxalate at said cathode; and (C) oxidizing said oxalate into said carbon dioxide at said anode. 

The method ... further comprising the step of: separating said carbon dioxide from said solution. 

The method ... wherein an energy consumed by said purifying of said carbon dioxide is less than 200,000 watt hours per ton of carbon dioxide.

(So, we're already much "less than" the above "500,000 watt hours per ton of carbon dioxide"; and, we still don't know just how much "less than 200,000 watt hours per ton of carbon dioxide" we can get.)

The method ... wherein said purification consumes approximately no additional water after said solution has been established in said electrochemical cell. 

The method ... wherein an electrical potential of said cathode is between zero volts and -1 volt. 

The method ... wherein said reducing uses a single electron per carbon atom.

(The two above claims actually highlight the efficiency of this process; and, make the "200,000 watt hours per ton of carbon dioxide" much easier to swallow. Such a small "electrical potential" can easily be generated by photovoltaic cells, much less wind- or hydro-power generators. And, the amount of electricity, one "electron per carbon atom" is the ultimate economy. In separate reports which we won't link to herein, we've already documented for you that we have rather impressive potentials for generating non-carbon wind, hydro and geothermal energy in the very heart of US Coal Country. Even more can be learned via:

West Virginia Department of Commerce Wind Energy; "The U.S. Department of Energy has determined that West Virginia has significant wind development opportunities"; and:

http://hydropower.inl.gov/resourceassessment/pdfs/states/wv.pdf; "U.S. Hydropower Resource Assessment
for West Virginia (USDOE)" wherein we learn that West Virginia, alone, has "37 identified sites" along her major rivers, the Ohio, Kanawha, Monongahela and Potomac, capable of generating in excess of  1,000 Megawatts of electricity, which would be, if our math consultant is correct, one billion Kilowatts, and, one trillion watts, each and every hour of every day, thus enabling, if we wished to develop the potential and direct it all to the process of our subject herein, "United States Patent Application 20110114501 - Purification of Carbon Dioxide from a Mixture of Gases", the recovery, even at the maximum "500,000 watt hours per ton of carbon dioxide", of two million tons of Carbon Dioxide - each and every hour of every day.

And, since, as we're told in:

West Virginia Carbon Dioxide Emissions by Sector; that:

West Virginia's Coal-fired electric power generation industry emits only "85 million tons" of Carbon Dioxide per year;

we could, in theory, via the realization and utilization of our full hydroelectric potentials, have our total, yearly West Virginia emissions of CO2 mopped up and ready for conversion, as via the process of the above-cited "United States Patent Application 20110114502 - Reducing Carbon Dioxide to Products", into "ethanol, ethylene, ... methane (and) methanol", in a shade less than two days; and, then, be on the phone to Pennsylvania, Ohio and Kentucky asking if they had any CO2 to spare.

Now, that's all as calculated and generalized for us, given our sadly limiting disabilities, by the owner of the restaurant where our benefactor works, who has to calculate and total all the receipts and balance the books at the end of each and every day. He's pretty good at it; but, someone should still check our numbers.

And, there is more to it, of course, such as the initial collection of CO2-containing gas, and it's transport to a centralized recycling and conversion facility. Still, the potentials, in combination with the processes of "United States Patent Application 20110114502 - Reducing Carbon Dioxide to Products" and "United States Patent Application 20100187123 - Conversion of Carbon Dioxide to Organic Products", as cited above, would seem to be rather enormous.)

Background and Field: The present invention relates to gas purification generally and, more particularly, to a method and/or apparatus for implementing purification of carbon dioxide from a mixture of gases. 

The combustion of fossil fuels in activities such as the electricity generation, transportation, and manufacturing produces billions of tons of carbon dioxide annually.

In order to capture carbon dioxide from industrial sources, such as a coal-fired power plant, the carbon dioxide is separated from flue gases, which are primarily nitrogen and water and include other trace gases, metals and particulates. Previous work in the field has many limitations, in particular the energy consumed in separating the carbon dioxide from the other gases and the amount of water used in the separation. A common technique currently available uses monoethyl amine (MEA) adsorption of the carbon dioxide from the flue gases. However, the technique utilizes high temperature steam to effectively separate the carbon dioxide from the amine. As such, the technique can consume as much as 30% of the energy generated at a coal-fired power plant. Furthermore, carbon dioxide capture increases both the amount of water that is brought into a power plant and the amount of water evaporated into the atmosphere by the power plant. Adding the carbon dioxide capture can increase the water brought into the power plant by 2300 to 4500 liters per megawatt-hour. Increased water evaporation from the power plant due to the carbon dioxide capture can range from 1900 to 3400 liters per megawatt-hour. 

Work has also been done on electrochemical systems, such as electrodialysis via carbonates, to separate the carbon dioxide from the other gases. The electrochemical systems have slow kinetics and low efficiency making the systems uneconomical. Membrane separation of the carbon dioxide is possible, but no effective membranes have been made to date. Carbon dioxide is also removed by cooling the flue gas until dry ice is formed. However, the energy used in the process is higher than for amine adsorption. 

Existing processes incorporating ethyl amines or other absorbents use large quantities of energy and water that make such techniques uneconomical. Membrane systems lack the strength and/or stability to last for long periods of time. Membrane systems and electrodialysis systems also have slow rates of reaction making upscaling difficult economically.

The present invention concerns a method for purification of carbon dioxide from a mixture of gases. The method generally includes steps (A) and (B). Step (A) may bubble the gases into a solution of an electrolyte and a catalyst in an electrochemical cell. The electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode generally reduces the carbon dioxide into one or more compounds. The anode may oxidize at least one of the compounds into the carbon dioxide. Step (B) may separate the carbon dioxide from the solution. 

The objects, features and advantages of the present invention include providing a method and/or apparatus for implementing purification of carbon dioxide from a mixture of gases that may (i) utilize lower amounts of energy than conventional techniques, (ii) provide reaction rates sufficiently high for scalability, (iii) provide stabile long-term reduction of carbon dioxide using copper-based alloys electrodes, (iv) provide for commercialization of electrochemical purification of carbon dioxide from a mixed gas and/or (v) consume little to no water in the purification chemistry.

Some embodiments of the present invention generally separate carbon dioxide from a mixture of gases using a reduction and oxidation process. The carbon dioxide may be isolated from the mixed gas by reducing the carbon dioxide to one or more compounds at a cathode. The compounds may include, but are not limited to oxalate, oxalate salts and/or organic acids. The organic acids may include, but are not limited to, oxalic acid, formic acid and glyoxylic acid. The compounds may be oxidized to form carbon dioxide at an anode. The resulting pure, or nearly pure, carbon dioxide may be subsequently collected for storage and/or other uses.

(Such "other uses" could include, as well, we submit, something like that disclosed in our report of:

Penn State Seeks CO2 Recycling Patent | Research & Development; concerning: "US Patent Application 20100213046 - Nanotube ... Photocatalytic Conversion of Carbon Dioxide; 2010; Assignee: The Penn State Research Foundation; Abstract: Nitrogen-doped titania nanotubes exhibiting catalytic activity on exposure to any one or more of ultraviolet, visible, and/or infrared radiation, or combinations thereof are disclosed. Also, methods are disclosed for use of nitrogen-doped titania nanotubes in catalytic conversion of carbon dioxide alone or in admixture with hydrogen-containing gases such as water vapor ... into products such as hydrocarbons and hydrocarbon-containing products".)

The purification of the carbon dioxide may be achieved efficiently in a divided electrochemical cell in which (i) a compartment contains an anode and (ii) another compartment contains a working cathode electrode and a catalyst. The compartments may be separated by an optional porous glass frit or other ion conducting bridge. Both compartments generally contain an aqueous solution of an electrolyte. A mixed gas containing the carbon dioxide may be continuously bubbled through the cathodic electrolyte solution to saturate the solution. 

The mixed gas may 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). Generally, the mixed gases may be obtained from concentrated point sources of generation prior to being released into the atmosphere. For example, high concentration carbon dioxide generally exists in flue gases of fossil fuel (e.g., coal, natural gas, oil, etc.) burning power plants. Emissions from varied industries, including geothermal wells, may also be captured on-site.

Various process conditions disclosed above, including electrolyte choice, cell voltage, and manner in which the mixed gas is bubbled, generally improve control of the reaction. Greater control over the reactions generally open the possibility for commercial systems that are modular and adaptable to different situations."

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One way to think of the above is an improvement on mining techniques - as if someone had come up with a way to cut the cost of mining Coal underground by half, or more.

Only, in this case, we would be efficiently collecting Carbon Dioxide from various exhaust streams, like those arising from separation and compression facilities associated with, as above, "natural gas wells", that is, "America's Clean Energy Alternative", and, making it readily available for conversion, as via, for just one other example, the process disclosed by:

Germany Awarded 2011 CO2 Recycling US Patent | Research & Development; concerning: "United States Patent 7,989,507 - Production of Fuel ... Utilizing Waste Carbon Dioxide; 2011; Assignee: Siemens Aktiengesellschaft (AG), Munich, Germany; Abstract: The present invention is directed to a method for utilizing CO2 waste comprising recovering carbon dioxide from an industrial process that produces a waste stream comprising carbon dioxide in an amount greater than an amount of carbon dioxide present in starting materials for the industrial process. The method further includes producing hydrogen using a renewable energy resource and producing a hydrocarbon material utilizing the produced hydrogen and the recovered carbon dioxide";

into "hydrocarbon material".

All of that is, of course, unless we would prefer, as now seems to be the case, to continue:

on in our economic enslavement to OPEC and Big Oil, and:

down what seems to be the current EPA path of destroying our economically essential Coal-based electrical power generation industry.

Continued public press whining about OPEC, the EPA, and the current Administration, and their vile intents, won't do a darned thing.

A little public press education, and consequent voter motivation, about the genuine, practical potentials, as shown herein, for efficiently reclaiming and productively recycling Carbon Dioxide, just might.


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