United States Patent Application: 0130199937
Our headline on this dispatch is, in some respects, misleading. It is certainly too narrow. The technology disclosed herein, as we will see, involves quite a lot more than the conversion of CO2 into just "Ethanol".By way of recap, we've so far provided you with numerous reports documenting the development of an integrated body of Carbon Dioxide chemical recycling technologies; which development, as seen for one example in:
West Virginia Coal Association | Princeton University November 20, 2012 CO2 to Ethanol | Research & Development; concerning: "United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products; November 20, 2012; Inventors: Andrew Bocarsly and Emily Barton Cole;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 ... . 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";
began in the Princeton University lab of Professor Andrew Bocarsly; and which, as seen for example in:
West Virginia Coal Association | New Jersey CO2 to High-Energy Alcohol | Research & Development; concerning: "United States Patent Application 20120132538 - Electrochemical Production of Butanol from Carbon Dioxide and Water; 2012; Inventors: Emily Barton Cole, Andrew Bocarsly, et. al., NJ and DC;
Abstract: Methods and systems for electrochemical production of butanol 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, a catalyst, and a cathode. Step (C) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to a product mixture. Step (D) may separate butanol from the product mixture"; and, in:
West Virginia Coal Association | New Jersey May 21, 2013, CO2 to Plastics Raw Materials | Research & Development; 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 co-producing a first product and a second product may include co-producing a glycol and an alkene employing a recycled halide. 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";continues to be advanced in what has been described as a "spin-off" company, "Liquid Light, Inc.", founded to further develop and commercialize the Carbon Dioxide-recycling technologies first established in Andrew Bocarsly's Princeton laboratory. More can be learned via:
Liquid Light Announces Issuance of Patent Covering Catalytic Carbon Dioxide Reduction Technology; "November 22, 2012; Liquid Light is a privately held corporation developing new catalysts and processes for the efficient and affordable conversion of carbon dioxide to a wide variety of high value chemicals. Our patented catalytic platform uses energy from any clean source (e.g. solar, wind, hydroelectric, and nuclear) to electrochemically drive the process", and:LIQUID LIGHT; "Liquid Light is the developer of technology that allows the efficient conversion of carbon dioxide to a wide variety of chemicals, fuels, and other compounds. Our patent-pending electrocatalytic platform leverages low-cost inputs with long-term pricing predictability and secure, domestic sources of energy to convert an industrial waste into a source of revenue"; and:
Liquid Light :: About; Liquid Light is an early-stage start-up founded on discoveries in the fields of catalysis and artificial photosynthesis from the research lab of Professor Andrew Bocarsly at Princeton University. We are developing highly efficient catalysts and chemical processes for converting carbon dioxide to fuels and industrial chemicals using no biological feedstocks. Liquid Light’s technology will allow transportation fuels and industrial chemicals to be made from waste carbon dioxide ... . Energy security, reductions in oil imports, and reductions in greenhouse gas emissions can be realized without major changes to existing infrastructure. Backed by Redpoint Ventures, we have started down the path to clean, secure energy. Dr. Andrew Bocarsly is a professor of chemistry at Princeton University and a founder of Liquid Light, where he serves as Chairman of the Scientific Advisory Board. A leading researcher in electrochemistry and renewable energy, he has worked for over 30 years on solar energy conversion, systems for energy storage and fuel cells. Dr. Bocarsly and his group at Princeton were the first in the world to develop a process for directly converting solar energy into liquid fuel using no additional energy source. He continues to work closely with Liquid Light developing new catalysts and systems for the efficient conversion of carbon dioxide to fuels and industrial chemicals".As we've gone along in the course of our reportage, we've documented many times, from many sources, as perhaps most definitively in:
West Virginia Coal Association | US Gov Confirms Coal Can Be A CO2-Neutral Source Of Power | Research & Development; concerning; "United States Patent 8,461,215 - Rendering Coal As An Environmentally Carbon Dioxide Neutral Fuel And A Regenerative Carbon Source; June 11, 2013; Inventors: George Olah and G.K. Surya Prakash, CA; Assignee: The University of Southern California; Abstract: The invention provides a method for rendering coal as an environmentally essentially carbon dioxide-neutral fuel. Carbon dioxide produced from coal combustion is captured, purified, combined with ... hydrogen, and reacted under reaction conditions sufficient to form methanol and/or dimethyl ether, which can be used as fuel or feedstock for derived synthetic hydrocarbons and products";
that, Carbon Dioxide, as perhaps conveniently reclaimed from economically essential facilities generating truly reliable and truly affordable electric power from our abundant domestic US Coal, can be converted into the fuel alcohol, Methanol, and into the substitute for both Diesel fuel and Liquefied Petroleum Gas, Dimethyl Ether.
Methanol, however, is not an ideal fuel alcohol for internal combustion engines, relative especially to the Butanol of the above-cited "United States Patent Application 20120132538 - Electrochemical Production of Butanol from Carbon Dioxide and Water; 2012"; and, relative even to that darling of the agricultural lobby, Ethanol.
Methanol has a lower energy density relative to those other alcohols; and, unlike Butanol, can be corrosive to some types of metal and plastic used in engine and fuel system manufacture.
Ethanol - - although it, like Methanol, exhibits, in high concentrations, similar metal and plastics corrosion effects - - derived from agricultural produce is of course widely touted as an alternative, renewable fuel that recycles, through the botanical process of photosynthesis, Carbon Dioxide.
One thing no one seems willing to expose, however, is the truth, that: through the use of mechanized, internal combustion engine-powered farming and harvesting, and, perhaps, fossil fuel-derived heat and electricity for subsequent processing; and, through the CO2-generating process of fermentation, the manufacture of Ethanol from agricultural produce both consumes more energy that it produces and generates more Carbon Dioxide than it recycles.
If we want and need Ethanol, and there are reasons why we would, since, as seen separately in:
Braskem Ethanol-to-Ethylene Plant, Triunfo, Rio Grande do Sul - Chemicals Technology; wherein it's related, that: "Brazilian petrochemical company Braskem inaugurated a new ethylene plant in Triunfo Petrochemical Complex in Triunfo municipality, in the Rio Grande do Sul state of Brazil in September 2010. The plant uses ethanol produced from sugarcane as the feedstock. It is the first large-scale ethylene project to use 100% renewable raw materials"; and, in:"United States Patent: 4138440 ; "United States Patent 4,138,440 - Conversion of Liquid Alcohols ... with ... ZSM-5 Catalyst; 1979; Assignee: Mobil Oil Corporation; Abstract: The conversion of alcohols and ethers to gasoline boiling constituents with HZSM-5 catalyst in a fluid catalyst system is arranged for reactant plug flow wherein the reaction temperature is controlled by the heat of vaporization of liquid reactant charged to the reactor. ... A method for converting a chemical reactant selected from the group consisting of methanol, ethanol, ether derivatives of lower alcohols and mixtures of alcohols and ethers to gasoline";
Ethanol, like Methanol, can be converted through known processes both into basic hydrocarbons, i.e., "ethylene", for the synthesis of certain commodity plastics, and into "gasoline", then, as seen in excerpts from the initial link in this dispatch, the Princeton University spin-off, Liquid Light, in an effort paid for by the United States Department of Energy, has developed the technology to synthesize, along with a number of other valuable and needed organic products, the alcohol, Ethanol, directly from Carbon Dioxide:
"United States Patent Application 20130199937 - Reducing Carbon Dioxide to Products
Patent US20130199937 - Reducing Carbon Dioxide to Products - Google Patents
Reducing Carbon Dioxide to Products - LIQUID LIGHT, INC.
Date: 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.
(Note the similarities in the description of this process and of that disclosed in Liquid Light's "United States Patent Application 20120132538 - Electrochemical Production of Butanol from Carbon Dioxide and Water". Also, in passing, as regards where Liquid Light might get the Carbon Dioxide with which to synthesize either Butanol or, as herein, as specified further on, Ethanol and associated products, we remind you of our report:
West Virginia Coal Association | New Jersey Reclaims CO2 for Hydrocarbon Synthesis | Research & Development; concerning: "United States Patent 8,500,987 - Purification of Carbon Dioxide from a Mixture of Gases; 2013; Inventors: Kyle Teamey, Emily Barton Cole, Narayanappa Sivasankar, Andrew Bocarsly, DC and NJ; Assignee: Liquid Light, Inc.; 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".
Further, we are obviously focusing the thesis of this dispatch on the conversion of Carbon Dioxide into, specifically, Ethanol, as a valuable liquid fuel commodity which nearly everyone is familiar with. However, as will be seen, just as with our above-cited report concerning: "United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products; November 20, 2012; Inventors: Andrew Bocarsly and Emily Barton Cole;Assignee: Princeton University"; Ethanol is only one of the products which is, or can be, synthesized from Carbon Dioxide using the technology and techniques disclosed herein. The important thing to note is that processing conditions can be varied to a certain extent so as to select more specifically for one product, or a range of products, to be synthesized from the CO2.)
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.
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 said products, and:
(iii) said cathode is selected from the group consisting of Al, Au, Ag, Bi, C, Cd, Co, Cr, Cu, a Cu alloy, Ga, Hg, In, Mo, Nb, Ni, NiCo2O4, a Ni alloy, a Ni--Fe alloy, Pb, Rh, Sn, a Sn alloy, Ti, V, W, Zn, Nichrome, austenitic steel, duplex steel, ferritic steel, martensitic steel, stainless steel ... and mixtures thereof;
(We'll interrupt to note, only once, that, as above and as will be made plain in the extended excerpts, a fairly wide range of elements and chemical compositions, some of them readily available in North America and relatively inexpensive, are suitable for use as both catalysts and as electrodes in this process. There are options which don't require the importation of exotic and costly materials.)
(B) adjusting 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; and:
(C) separating said products from said solution.
(Note, in the above, as per our earlier comment, indication that processing conditions can be varied, or adjusted, so as to influence and control "which of said products is produced". Again: Ethanol is not the only product which can be, using the technology disclosed herein, made from Carbon Dioxide.)
The method ... wherein said catalyst is one or more of adenine, an amine containing sulfur, an amine containing oxygen, an azole, benzimidazole, a bipyridine, furan, an imidazole, an imidazole-related species with at least one five-member ring, an indole, methylimidazole, an oxazole, phenanthroline, pterin, pteridine, a pyridine, a pyridine-related species with at least one six-member ring, pyrrole, quinolone, and a thiazole.
The method ... wherein said products comprise one or more of acetaldehyde, acetate, acetic acid, acetone, 1-butanol, 2-butanol, 2-butanone, carbon, carbon monoxide, carbonates, ethane, ethanol, ethylene, formaldehyde, formate, formic acid, glycolate, glycolic acid, glyoxal, glyoxylate, glyoxylic acid, graphite, isopropanol, lactate, lactic acid, methane, methanol, oxalate, oxalic acid, a polymer containing carbon dioxide, 1-propanal, 1-propanol, and propionic acid.
(Although we are focusing on the production of Ethanol as the theme of this report, note how variations in the catalyst and in the cathode material, and, as following, the composition of the electrolyte, can enable the production of a wide range of Carbon-containing compounds from Carbon Dioxide.)
The method ... wherein said electrolyte is at least one of Na2SO4, KHCO3, KCl, NaNO3, NaCl, NaF, NaClO4, KClO4, K2SiO3, CaCl2, a ... halide ion, an alkyl amine, a borate, a carbonate, a guanidinium derivative, a nitrite, a nitrate, a phosphate, a polyphosphate, a perchlorate, a silicate, a sulfate, and a tetraalkyl ammonium salt (and) 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) to avoid contact with said cathode.
The method ... wherein said pH level is between approximately 1 and approximately 8 (and) wherein said electrical potential is between approximately -0.7 volts and -2 volts.
(As above, not a lot of electrical potential is needed to power the Carbon Dioxide conversion. The implication could be that this is an efficient and cost-effective process.)
The method ... further comprising a homogenous catalyst in the second cell compartment (and) wherein said homogenous catalyst is one or more of adenine, an amine containing sulfur, an amine containing oxygen, an azole, benzimidazole, a bipyridine, furan, an imidazole, an imidazole-related species with at least one five-member ring, an indole, methylimidazole, an oxazole, phenanthroline, pterin, pteridine, a pyridine, a pyridine-related species with at least one six-member ring, pyrrole, quinolone, and a thiazole.
A system for electrochemical reduction of carbon dioxide, comprising: an electrochemical cell including: 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, said second cell compartment containing an electrolyte; a cathode positioned within said second cell compartment, said cathode selected from the group consisting of n-GaAs, SS304, n-Ge, NiCo2O4, Rh, and mixtures thereof; and an energy source operably coupled with said anode and said cathode, said energy source 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.
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 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, NiCo2O4, 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.
Carbon dioxide may be efficiently converted to value-added products, using either a minimum of electricity (that may be generated from an alternate energy source) or directly using visible light.
Some processes described above may generate high energy density fuels that are not fossil-based as well as being chemical feedstock that are not fossil or biologically based.
Moreover, the catalysts for the processes may be substituents-sensitive and provide for selectivity of the value-added products.
The organic products may include, but are not limited to, acetaldehyde, acetone, carbon, carbon monoxide, carbonates, ethanol, ethylene, formaldehyde, formic acid, glyoxal, glyoxylic acid, graphite, isopropanol, methane, methanol, oxalate, oxalic acid. Inorganic products may include, but are not limited to, polymers containing carbon dioxide. Specific process conditions may be established that maximize the carbon dioxide conversion to specific chemicals beyond methanol."
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Again, to beat it to death, a lot of things besides Ethanol, and Methanol, can be made, using the variations of the technology delineated herein, from Carbon Dioxide.
In essence, "United States Patent Application 20130199937 - Reducing Carbon Dioxide to Products" encapsulates a description of technology developed in part with funding provided by our tax dollars, via "Grant DE-SC0006201 awarded by the Department of Energy", which technology enables us to, as it were, "redefine" Carbon Dioxide.
Like natural petroleum, Carbon Dioxide can now be seen and treated as a valuable basic natural resource; a natural raw material from which we can extract, or synthesize, virtually any and all types of organic "Products", including, among others, "polymers", substitute natural gas "methane", and the fuel alcohols "methanol" and "ethanol".
And, using the catalysts and catalytic processes identified herein by Liquid Light, such transmutations can be accomplished "using either a minimum of electricity (that may be generated from an alternate energy source) or directly using visible light".
We don't wish to distract from the profound accomplishments of Liquid Light in establishing such Carbon Dioxide utilization technologies; but, to emphasize the point, we refer you to our recent report of:
West Virginia Coal Association | August 13, 2013 Power Plant CO2 to High-Octane Gasoline | Research & Development; concerning: "US Patent 8,506,910 - Process and System for Producing Liquid Fuel from Carbon Dioxide and Water; August 13, 2013; Assignee: CRI Ehf, Iceland; Abstract: A process and system for producing high octane fuel from carbon dioxide and water is disclosed. The feedstock for the production line is industrial carbon dioxide and water, which may be of lower quality. The end product can be high octane gasoline, high cetane diesel or other liquid hydrocarbon mixtures suitable for driving conventional combustion engines";wherein yet another accomplished band of scientists, in another nation, using a different technical process, confirm that we can now, we here insist that we should now, begin to view and treat the Carbon Dioxide that is fortuitously co-produced by our use of Coal in the generation of genuinely abundant and truly affordable electric power as what it actually is, i.e.:
A valuable, maybe even a precious, resource; a natural resource from which we can, using freely-available environmental energy, such as "visible light", convert into anything, quite literally anything, we now not only blow our national wealth to purchase from the sometimes unfriendly nations of OPEC, but, which we also waste the lives of young Americans in uniform to defend and secure our supply of.
The technology is here; the technology is available. The only thing we apparently lack is the public intellect to recognize it, the public courage to announce it, and, the public will to get off our dead cans and put it, along with more of our fellow US citizens, to work.