United States Patent: 8845878

 
First, it isn't the USDOE directly who have, in this case at least, figured out how to produce valuable "Products" from Carbon Dioxide, as we might recover from the flue-gases resulting from our economically essential use of Coal in the generation of genuinely abundant and truly affordable electric power.

It is, instead, a team of scientists with such a well-established and demonstrated expertise in the development of Carbon Dioxide utilization technologies that, as will be seen, the United States Department of Energy who, as seen for just one example in:

USDOE Solar Thermochemical CO2-to-Fuel | Research & Development | News; concerning: "Solar Fuel Production Through The Thermochemical Decomposition of Carbon Dioxide'; Nathan P. Siegel, et. al.,  Sandia National Laboratories (USDOE), Albuquerque, NM; Abstract: Solar energy systems based on an intermittent resource benefit from an energy storage mechanism that decouples the solar resource from the load, enabling operation when the resource is unavailable. ... Storing solar energy in the form of chemical fuels offers another more energy dense storage mechanism that enables the utilization of solar energy to address the energy needs of the transportation sector. Concentrating solar power (CSP) systems are capable of operating at the elevated temperatures needed to drive thermochemical reactions that convert the stable combustion products, carbon dioxide and water, first into synthesis gas, a mixture of carbon monoxide and hydrogen, and then into liquid hydrocarbon fuels such as methanol, gasoline, and jet fuel";

have a demonstrated and hugely-commendable interest in the development of CO2-utilization technology in their own laboratories, likely had little hesitation about funding these scientists' further efforts in establishing  processes for using Carbon Dioxide as the initial source material for manufacturing a broad range of what we might think of as "petrochemicals", that is, organic compounds which themselves are already established as the key raw materials in industries that currently manufacture plastics, polymers and other immensely valuable materials for commerce and industry.

Second, we remind you of the Carbon Dioxide utilization technologies developed in the Princeton University laboratories of Professor Andrew Bocarsly, as in perhaps our most recent report of their achievements:  

Princeton University March, 2014, CO2 to Methanol | Research & Development | News; concerning: "United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products; 2014; Inventors: Andrew Bocarsly, NJ, and Emily Barton Cole, TX; 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: An environmentally beneficial method of producing methanol by electrochemical reduction of any available source of carbon dioxide".

Note, in the above exposition of "United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products", that, although the Princeton processes which convert Carbon Dioxide into "Organic Products" are "electrochemical" in nature, the amount of electricity required is low enough that it can, by implication, be supplied by relatively low-power photo-voltaic sources, and, thus, the potential for "photoelectrochemically reducing the carbon dioxide", in a process which we might think of as form of "artificial photosynthesis".

Such artificial photosynthesis could be used as a means of taking genuine advantage of intermittent solar energy, by storing it in chemical form via the recycling of Carbon Dioxide into fuels and chemicals. Thus, solar-generated electricity, which is too fickle and too low-power to make genuine contributions to the electrical grid, could be stored and accumulated in the form of various fuel compounds, such as "methanol", via the consumption and chemical conversion of Carbon Dioxide.

As we've seen in other reports, such as:

New Jersey May 21, 2013, CO2 to Plastics Raw Materials | Research & Development | News; concerning: "United States Patent 8,444,844 - Electrochemical Co-production of a Glycol and an Alkene Employing Recycled Halide; May 21, 2013; Inventors: Kyle Teamey, DC, Jerry Kaczur, FL, and Emily Barton Cole, TX; Assignee: Liquid Light, Inc., NJ; Abstract: The present disclosure is a method and system for electrochemically co-producing a first product and a second product. The system may include a first electrochemical cell, a first reactor, a second electrochemical cell, at least one second reactor, and at least one third reactor. The method and system for for co-producing a first product and a second product may include co-producing a glycol and an alkene employing a recycled halide, Claims: A method for co-producing a first product and a second product, the method comprising the steps of: contacting a first region of a first electrochemical cell having an cathode with a catholyte comprising carbon dioxide; contacting a second region of a first electrochemical cell having an anode with an anolyte comprising a MX where M is at least one cation and X is selected from a group consisting of Fluorine, Chlorine, Bromine, Iodine, and mixtures thereof; applying an electrical potential between the anode and the cathode sufficient to produce M-carboxylate recoverable from the first region of the first electrochemical cell and a halogen recoverable from the second region of the first electrochemical cell; reacting the M-carboxylate with HX via a secondary reactor to produce a carboxylic acid and MX, the MX being recycled to an input of the second region of the first electrochemical cell; contacting a first region of a second electrochemical cell having a cathode with a catholyte comprising the carboxylic acid; contacting a second region of a second electrochemical cell having an anode with an anolyte comprising HX; applying an electrical potential between the anode of the second electrochemical cell and the cathode of the second electrochemical cell sufficient to produce at least one of another carboxylic acid, an aldehyde, a ketone, a glycol or an alcohol recoverable from the first region of the second electrochemical cell and a halogen recoverable from the second region of the second electrochemical cell; reacting the halogen from the second region of the first electrochemical cell and from the second region of the second electrochemical cell with an alkane, aromatic compound, or other carbon compound to produce a halogenated compound and HX, the HX being recycled back to the second region of the second electrochemical cell and to the input of the secondary reactor; and reacting the halogenated compound via at least one reactor to produce at least one of an alkene, alkyne, alcohol, phenol, aldehyde, ketone, unsaturated carbon compound, or longer-chain alkane"; and:

Jersey Converts More CO2 into High-Value Products | Research & Development | News; concerning: "United States Patent 8,592,633 - Reduction of CO2 to Carboxylic Acids, Glycols and Carboxylates; November 26, 2013; Inventors: Emily Barton Cole, Kyle Teamey, Andrew Bocarsly, and Narayanappa Sivasankar, NJ and DC; Assignee: Liquid Light, Incorporated, NJ; Abstract: Methods and systems for electrochemical conversion of carbon dioxide to carboxylic acids, glycols, and carboxylates are disclosed. A method may include, but is not limited to, steps (A) to (D). Step (A) may introduce water to a first compartment of an electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a solution of an electrolyte and a cathode. Step (C) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient to reduce the carbon dioxide to a carboxylic acid intermediate. Step (D) may contact the carboxylic acid intermediate with hydrogen to produce a reaction product";

the company "Liquid Light, Incorporated" - - which has been described as a corporate "spin-off" founded on the Carbon Dioxide utilization efforts undertaken in the Princeton University labs of Dr. Bocarsly, a spin-off intended to further develop and to commercialize Princeton's achievements in CO2 utilization, and in which company Bocarsly's Princeton protege, Emily Barton Cole, and perhaps Bocarsly himself, participate as principals - - has, indeed, continued to develop those CO2 utilization processes, and has refined them to such a degree that a far broader range of organic compounds can be synthesized on a practical basis from Carbon Dioxide.

As indicated, those organic compounds can be seen and treated as, indeed are chemically identical to, organic chemicals conventionally derived from natural petroleum and used industrially as the starting materials from which immensely valuable products like plastics and polymers are manufactured.

Another of Liquid Light's technologies for the use and consumption of CO2 in the "photoelectrochemical" synthesis of what we might think of as "petro-chemicals" was disclosed in our report of:

The USDOE and New Jersey Convert CO2 into Ethanol | Research & Development | News; concerning: "United States Patent Application 20130199937 - Reducing Carbon Dioxide to Products; August 8, 2013; Inventors: Emily Barton Cole, et. al., Texas and New Jersey; Assignee: Liquid Light, Inc., NJ; Abstract: A method reducing carbon dioxide to one or more products may include steps (A) to (C). Step (A) may bubble said carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell. The divided electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode may reduce said carbon dioxide into said products. Step (B) may adjust one or more of (a) a cathode material, (b) a surface morphology of said cathode, (c) said electrolyte, (d) a manner in which said carbon dioxide is bubbled, (e), a pH level of said solution, and (f) an electrical potential of said divided electrochemical cell, to vary at least one of (i) which of said products is produced and (ii) a faradaic yield of said products. Step (C) may separate said products from said solution. Government Interests: This invention was made with government support under Grant DE-SC0006201 awarded by the Department of Energy. The government has certain rights in the invention".

And, herein we learn that technical experts in the employ of our United States Government's Patent and Trademark Office quite recently validated the practicability of the Carbon Dioxide utilization technology disclosed in the above "United States Patent Application 20130199937", through their allowance and issuance of, as excerpted from the initial link in this dispatch:

"United States Patent 8,845,878 - Reducing Carbon Dioxide to Products

Reducing carbon dioxide to products - Liquid Light, Inc.

September 30, 2014

Inventors: Emily Barton Cole, et. al., Texas and New Jersey

Assignee: Liquid Light, Incorporated, Monmouth Junction, NJ

Abstract: A method reducing carbon dioxide to one or more products may include steps (A) to (C). Step (A) may bubble said carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell. The divided electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode may reduce said carbon dioxide into said products. Step (B) may adjust one or more of (a) a cathode material, (b) a surface morphology of said cathode, (c) said electrolyte, (d) a manner in which said carbon dioxide is bubbled, (e), a pH level of said solution, and (f) an electrical potential of said divided electrochemical cell, to vary at least one of (i) which of said products is produced and (ii) a faradaic yield of said products. Step (C) may separate said products from said solution.

Government Interests: This invention was made with government support under Grant DE-SC0006201 awarded by the Department of Energy. The government has certain rights in the invention.

(At roughly this point in United States Patent publications, between the Abstract and the statement, if any, of government interests, US Patents that disclose related and precedent technical art, and publications making report of supporting observations, experiments, etc., are catalogued. And, as we've noted once or twice previously in our reports concerning Liquid Light, their lists of references are extensive and comprehensive. They speak of diligent and meticulous scholarship on the part of Liquid Light, in addition to the experimentation and development that went into the current innovation. The science behind this CO2 utilization technology seems rock solid, and, we are led to conclude unimpeachable. We recommend that interested readers access the full Patent document via, especially, the USPTO's primary link, if it retains functionality, and have a look at that documentation.)

Claims: A method for reducing carbon dioxide to one or more products, comprising:

(A) bubbling said carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell, wherein (i) said divided 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 carbon monoxide, and (iii) said catalyst is a homogeneous heterocyclic amine catalyst and said cathode is selected from the group consisting of Alumiunum, Gold, Silver, Bismuth, Carbon, (and others speficied; and,)

(B) separating said carbon monoxide from said solution. 

The method ... wherein said homogeneous heterocyclic amine catalyst is one or more of adenine, an amine containing sulfur, an amine containing oxygen, (and/or others specified). 

The method ... wherein said electrolyte is at least one of Sodium Sulfate, Potassium Bicarbonate (or others specified). 

The method ... further comprising: introducing to said solution of said electrolyte at least one of a divalent cation including at least one of calcium, magnesium, or zinc. 

The method ... wherein said manner in which said carbon dioxide is bubbled comprises: bubbling said carbon dioxide to contact said cathode (or) wherein said manner in which said carbon dioxide is bubbled comprises: bubbling said carbon dioxide to avoid contact with said cathode. 

The method ... wherein said solution has a pH between approximately 1 and approximately 8. 

The method ... wherein the cathode has a potential of -1 to -1.4 volts vs SCE (and) wherein the solution has a pH of 5 to 7. 

(The above "SCE" is a "saturated calomel electrode". And, it is simply a "reference" against which electric currents are measured. For more about it all than you likely want to know, check out the explanation and the catalogue of additional reference links accessible via:

http://en.wikipedia.org/wiki/Reference_electrode.

The point is, this process technology doesn't require a lot of juice, "-1 to -1.4 volts", to convert Carbon Dioxide in one of the specified electrolyte solutions into, at least, the above-specified, chemically reactive "carbon monoxide". That's a pretty low energy requirement, and, as Liquid Light eventually points out, it could easily be met by the low-level and intermittent power generated by what are too-loosely labeled "renewable" sources, like wind or solar.)

Background and Field: The present invention relates to chemical reduction generally and, more particularly, to a method and/or apparatus for implementing reducing carbon dioxide to products. 

A mechanism for mitigating emissions (of CO2) is to convert carbon dioxide into economically valuable materials such as fuels and industrial chemicals.

If the carbon dioxide is converted using energy from renewable sources, both mitigation of carbon dioxide emissions and conversion of renewable energy into a chemical form that can be stored for later use will be possible.

Electrochemical and photochemical pathways are means for the carbon dioxide conversion.

Summary: The present disclosure concerns methods for reducing carbon dioxide to one or more products. The methods may include steps (A) to (C).

Step (A) may bubble the carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell. The divided 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 the products.

Step (B) may adjust one or more of (a) a cathode material, (b) a surface morphology of said cathode, (c) said electrolyte, (d) a manner in which said carbon dioxide is bubbled, (e), a pH level of said solution, and (f) an electrical potential of said divided electrochemical cell, to vary at least one of (i) which of said products is produced and (ii) a faradaic yield of said products.

Step (C) may separate the products from the solution. 

The present disclosure concerns a system for electrochemical reduction of carbon dioxide. The system may include an electrochemical cell, which may include a first cell compartment, an anode positioned within said first cell compartment, a second cell compartment, a separator interposed between said first cell compartment and said second cell compartment. The second cell compartment may contain an electrolyte. The electrochemical cell may include a cathode within said second cell compartment. The cathode may be selected from the group consisting of n-GaAs, SS304, n-Ge, NiCo.sub.2O.sub.4, Rh, and mixtures thereof. The system may also include an energy source operably coupled with said anode and said cathode. The energy source may be configured to apply a voltage between said anode and said cathode to reduce carbon dioxide at said cathode to at least one of acetate, acetic acid, glycolate, and glycolic acid. 

Summary: In accordance with some embodiments of the present invention, an electro-catalytic system is provided that generally allows carbon dioxide to be converted at modest overpotentials to highly reduced species in an aqueous solution. Some embodiments generally relate to simple, efficient and economical conversion of carbon dioxide to reduced organic products, such as methanol, formic acid and formaldehyde. Inorganic products such as polymers may also be formed.

Carbon-carbon bonds and/or carbon-hydrogen bonds may be formed in the aqueous solution under mild conditions utilizing a minimum of energy. In some embodiments, the energy used by the system may be generated from an alternative energy source or directly using visible light, depending on how the system is implemented

The electrical energy for the electrochemical reduction of carbon dioxide may come from a normal energy source ... and alternatives (e.g., hydroelectric, wind, solar power, geothermal, etc.), from a solar cell or other nonfossil fuel source of electricity, provided that the electrical source supply at least 1.6 volts across the cell. Other voltage values may be adjusted depending on the internal resistance of the cell employed. 

Advantageously, the carbon dioxide 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). Most suitably, the carbon dioxide may be obtained from concentrated point sources of generation prior to being released into the atmosphere.

For example, high concentration carbon dioxide sources may frequently accompany natural gas in amounts of 5% to 50%, exist in flue gases of fossil fuel (e.g., coal, natural gas, oil, etc.) burning power plants and nearly pure carbon dioxide may be exhausted from cement factories and from fermenters used for industrial fermentation of ethanol. Certain geothermal steams may also contain significant amounts of carbon dioxide. The carbon dioxide emissions from varied industries, including geothermal wells, may be captured on-site. Separation of the carbon dioxide from such exhausts is known. Thus, the capture and use of existing atmospheric carbon dioxide in accordance with some embodiments of the present invention generally allow the carbon dioxide to be a renewable and unlimited source of carbon".

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

We'll close there to emphasize a few points.

In essence, this is a process that will enable low-level electricity acquired from various "alternative" sources, i.e., "wind, solar", to convert Carbon Dioxide - - acquired, perhaps, from such abundant sources as "natural gas wells", where the gas is stripped of it's quite-often very high load of naturally-occurring CO2 prior to being put in a pipeline, or, one of the environmentalist darlings, "geothermal ... wells", since an inconvenient truth about "geothermal" water solutions is that they are often absolutely loaded with CO2 and fizz like Perrier(r) when the pressure on them is removed - - into a variety of valuable chemical products and chemical product precursors.  

And, although "carbon monoxide" is specified in the Claims section as, perhaps, a predominant product, as Liquid Light specifies, changes in electrode and electrolyte materials, and certain process conditions, can as well, in certain "embodiments", enable the production, from Carbon Dioxide, of "methanol, formic acid and formaldehyde. Inorganic products such as polymers may also be formed".

And, those products, in this process, are formed rather directly from Carbon Dioxide, as opposed to, as in the earlier-cited USDOE report:

"Solar Fuel Production Through The Thermochemical Decomposition of Carbon Dioxide'; Nathan P. Siegel, et. al.,  Sandia National Laboratories (USDOE), Albuquerque, NM; Abstract: Solar energy systems based on an intermittent resource benefit from an energy storage mechanism that decouples the solar resource from the load, enabling operation when the resource is unavailable. ... Concentrating solar power (CSP) systems are capable of operating at the elevated temperatures needed to drive thermochemical reactions that convert the stable combustion products, carbon dioxide and water, first into synthesis gas, a mixture of carbon monoxide and hydrogen, and then into liquid hydrocarbon fuels such as methanol, gasoline, and jet fuel";

a process wherein CO2 and H2O are first converted together into hydrocarbon "synthesis gas", which is then catalytically, chemically condensed into such seemingly-needful things as "gasoline and jet fuel".

However, we'll note, that, as seen in our report of:

New Jersey May 13, 2014, CO2 to Hydrocarbon Synthesis Gas | Research & Development | News; concerning: "United States Patent 8,721,866- Electrochemical Production of Synthesis Gas from Carbon Dioxide; May 13, 2014; Inventors: Narayanappa Sivasankar, Emily Barton Cole, Kyle Teamey, NJ and DC; Assignee: Liquid Light, Inc., NJ; Abstract: A method for electrochemical production of synthesis gas from carbon dioxide is disclosed. The method generally includes steps (A) to (C). Step (A) may bubble the carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell. The divided 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 a plurality of components. Step (B) may establish a molar ratio of the components in the synthesis gas by adjusting at least one of (i) a cathode material and (ii) a surface morphology of the cathode. Step (C) may separate the synthesis gas from the solution";

Liquid Light Incorporated has that option covered, as well. More confirmation of the value of such CO2-derived "Synthesis Gas', or syngas, can be learned via:

SynGas Applications | Saint-Gobain NorPro; "SynGas, H2 + CO, is the direct end product of gasification and is used as an intermediary building block for the final production (synthesis) of various fuels such as synthetic natural gas, ammonia, methanol, and synthetic petroleum fuel".

In sum, Carbon Dioxide, as it arises in only a small way, relative to some all-natural and un-taxable sources of it's emission, such as the Earth's inexorable processes of planetary volcanism, from our essential use of Coal in the generation of abundant, reliable and affordable electric power, can be seen and treated as  valuable raw material resource from which, in processes powered by "environmental energy", we can manufacture a full range of products, including fuel alcohols and "polymers", we conventionally and currently derive from natural petroleum.

Thus, not only could we begin to free ourselves from our economic bondage to, our crippling dependence on, OPEC, we could also free our economically vital Coal-mining and Coal-use industries from, as seen in:

EPA proposes cutting carbon dioxide emissions from coal plants 30% by 2030 - The Washington Post; "Under the draft rule, the EPA would let states and utilities meet the new standard with different approaches mixing four options including energy efficiency, shifting from coal to natural gas, investing in renewable energy and making power plant upgrades. Other compliance methods could include offering discounts to encourage consumers to shift electricity use to off-peak hours";

duplicitous sanctions based on, as explained in our earlier discourse, utterly false, but nonetheless popularly fostered, mythologies about the relative contributions by "coal" and "natural gas", used in the generation of electricity, of Carbon Dioxide to the environment. 

Carbon Dioxide, as confirmed herein by one branch of our United States Government, via their recent allowance of our subject herein, "United States Patent 8,845,878 - Reducing Carbon Dioxide to Products", is a valuable raw material resource; a resource which can be harvested, even "from the atmosphere itself", and then be converted, via a process relying, for example, on "wind" or "solar" electricity to power it, into such industrially-useful products as "acetate, acetic acid, glycolate, and glycolic acid", and other valuable commodities, like "methanol, formic acid and formaldehyde", and, even, "polymers".

Somebody, somewhere, needs to scrape together the integrity to start broadcasting that truth, not just to United States Coal Country, but, to the entire United States of America. Every single United States citizen, except maybe for the holders of stock in Big Oil, would benefit from implementation of the knowledge.


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