Before getting to our primary subject herein, we remind you of our many previous reports on the Carbon Dioxide-recycling New Jersey company, "Liquid Light, Incorporated", which company was founded on the CO2-utilization technologies initially established, with some of the development funded by our United States Government, in the Princeton University labs of Professor Andrew Bocarsly, about whom we've reported, 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; 2012; Inventors: Andrew Bocarsly and Emily Barton Cole, NJ;Assignee: Princeton University, NJ; Abstract: The invention relates to various embodiments of an environmentally beneficial method for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in a divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor cathode electrode in another cell compartment that also contains an aqueous solution of an electrolyte and a catalyst of one or more substituted or unsubstituted aromatic amines to produce therein a reduced organic product. Government Interests: This invention was made with United States government support from National Science Foundation Grant No. CHE-0616475. The United States Government has certain rights in this invention. Claims: A method of converting carbon dioxide to provide at least one product selected from the group consisting of glyoxal, isopropanol, ethanol".
"Liquid Light, Incorporated" was, as seen separately in:
Princeton University - Startup born in Princeton lab turns carbon dioxide into fuels; concerning: "'Startup born in Princeton lab turns carbon dioxide into fuels'; June 14, 2012; Ask Andrew Bocarsly about the innovation behind Liquid Light, a New Jersey startup company that turns carbon dioxide into fuels and industrial chemicals, and the Princeton University chemistry professor smiles ruefully. 'The project goes back to the early '90s,' he said. "But nobody cared about carbon dioxide at that time.' Today, carbon dioxide (CO2) is a hot topic. Scientists around the globe are searching for ways to store, dispose of, or prevent the formation of the greenhouse gas, which is a major driver of global climate change. Liquid Light hopes to take this concept one step further and harness waste CO2 as a source of carbon to make industrial chemicals and fuels. The technology behind the process is simple: Take CO2 and mix it in a water-filled chamber with an electrode and a catalyst. The ensuing chemical reaction converts CO2 into a new molecule, methanol, which can be used as a fuel, an industrial solvent or a starting material for the manufacture of other chemicals. Liquid Light's founders include Bocarsly and his former graduate student Emily Cole, who earned her Ph.D. from Princeton in 2009. Cole helped revive efforts in Bocarsly's lab to study the conversion of CO2 into usable fuels, which led to the launch of Liquid Light and an ongoing collaboration that Bocarsly said has been extremely positive for his research team at the University. Bocarsly likes to call (their) process "reverse combustion" because it is like running a burning reaction backwards. Instead of burning fuel and oxygen to produce CO2, the CO2 converts back into fuel and oxygen. The research has received funding from the Air Force Office of Scientific Research (AFSOR), the National Science Foundation and the Department of Energy (DOE). The collaboration between Liquid Light and the University was supported by the DOE Small Business Innovation Research program and the AFOSR Small Business Technology Transfer program. Princeton's agreement with Liquid Light allowed the company to continue to collaborate with Bocarsly and his research team. Before long, new discoveries were emerging. "They started noticing interesting chemistry that we wouldn't have predicted," said Bocarsly. The Princeton scientists did some additional studies, and made a surprising discovery: They could turn CO2, which contains only one carbon, into a compound with a carbon-carbon bond, which vastly increases the possibilities for creating commercial applications. This was radical because although the reaction is certainly possible, it is highly unlikely to happen because so many other competing reactions are occurring. One of the chemicals Liquid Light can make is isopropanol, commonly known as rubbing alcohol and an important industrial chemical. Another is butanol, which could be commercially important as a fuel. Liquid Light's technology offers the potential to make these chemicals at lower cost than today's methods, which involve starting with fossil fuels such as petroleum and natural gas";established to further advance and to commercialize Princeton University's CO2 utilization technologies, which, as seen for one example in our report of:
West Virginia Coal Association | New Jersey Converts CO2 and Nitrogen Oxides into Fertilizer | Research & Development; concerning: "United States Patent 8,524,066 - Electrochemical Production of Urea from NOx and Carbon Dioxide; September 3, 2013; Inventors: Narayanappa Sivasankar, et. al., NJ; Assignee: Liquid Light Inc., NJ; Abstract: Methods and systems for electrochemical production of urea are disclosed. A method may include, but is not limited to, steps (A) to (B). Step (A) may introduce carbon dioxide and NOx to a solution of an electrolyte and a heterocyclic catalyst in an 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 the carbon dioxide and the NOx into a first sub-product and a second sub-product, respectively. Step (B) may combine the first sub-product and the second sub-product to produce urea";
they have done.
And, herein we learn that Liquid Light, and Princeton University scientists Bocarsly and Cole, and others, are continuing to advance the technology for efficiently utilizing and consuming CO2 in the electrochemical synthesis of various organic chemicals; in this case organic compounds which can be used as intermediates or raw materials in the further, economical, synthesis of high-value products.
As seen in excerpts from the initial link in this dispatch to the recent:
"United States Patent 8,592,633 - Reduction of CO2 to Carboxylic Acids, Glycols and Carboxylates
Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates - Liquid Light, Inc.
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,
(Note "Step (D)", as above. That's where things get more interesting, as seen further on.)
Claims: A method for electrochemical conversion of carbon dioxide, comprising: (A) introducing a liquid to a first compartment of an electrochemical cell, the first compartment including an anode; (B) introducing carbon dioxide to a second compartment of the electrochemical cell, the second compartment including a solution of an electrolyte, a cathode, and a homogenous heterocyclic amine catalyst, wherein each bond of the homogenous heterocyclic amine catalyst is selected from the group consisting of: a carbon-carbon bond, a carbon-hydrogen bond, a carbon-nitrogen bond, a carbon-oxygen bond, a carbon-sulfur bond, a nitrogen-hydrogen bond, a nitrogen-nitrogen bond, a nitrogen-oxygen bond, and an oxygen-hydrogen bond; (C) applying an electrical potential between the anode and the cathode sufficient for the cathode to reduce the carbon dioxide to at least a carboxylate; (D) acidifying the carboxylate to convert the carboxylate into a carboxylic acid; (E) extracting the carboxylic acid; and (F) contacting the carboxylic acid with hydrogen to form a reaction product.The method ... wherein the carboxylate includes at least one of formate, glycolate, glyoxylate, lactate, or oxalate (and/or) at least one of formic acid, glycolic acid, glyoxylic acid, lactic acid, or oxalic acid (and)wherein the reaction product includes at least one of formaldehyde, methanol, glycolic acid, glyoxal, glyoxylic acid, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, ethanol, propylene glycol, or isopropanol.
The method ... wherein the carboxylate includes formate, the carboxylic acid includes formic acid, and the reaction product includes at least one of formaldehyde or methanol.
The method ... wherein the carboxylate includes oxalate, the carboxylic acid includes oxalic acid, and the reaction product includes at least one of glyoxylic acid, glycolic acid, glyoxal, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, or ethanol.
The method ... wherein the carboxylate includes lactate, the carboxylic acid includes lactic acid, and the reaction product includes at least one of propylene glycol or isopropanol.
Background and Field: The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical production of carboxylic acids, glycols, and carboxylates from carbon dioxide.
Summary: The present invention is directed to using particular cathode materials, homogenous heterocyclic amine catalysts, and an electrolytic solution to reduce carbon dioxide to a carboxylic acid intermediate preferably including at least one of formic acid, glycolic acid, glyoxylic acid, oxalic acid, or lactic acid. The carboxylic acid intermediate may be processed further to yield a glycol-based reaction product. The present invention includes the process, system, and various components thereof.
In certain preferred embodiments, the reduction of the carbon dioxide to produce carboxylic acid intermediates, carboxylic acids, and glycols may be preferably achieved in a divided electrochemical or photoelectrochemical cell having at least two compartments. One compartment contains an anode suitable to oxidize water, and another compartment contains a working cathode electrode and a homogenous heterocyclic amine catalyst. The compartments may be separated by a porous glass frit, microporous separator, ion exchange membrane, or other ion conducting bridge. Both compartments generally contain an aqueous solution of an electrolyte. Carbon dioxide gas may be continuously bubbled through the cathodic electrolyte solution to preferably saturate the solution or the solution may be pre-saturated with carbon dioxide.
(Note, in the above, specification of "an anode suitable to oxidize water", which is how the Hydrogen is made available for recombination with the Carbon from Carbon Dioxide. We've explained what it means to "oxidize water", for the generation of both Hydrogen and Oxygen from Water, previously. For a full description, see:
Heterogeneous water oxidation - Wikipedia, the free encyclopedia .)
Advantageously, the carbon dioxide may be obtained from any source (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 high purity carbon dioxide may be exhausted from cement factories, from fermenters used for industrial fermentation of ethanol, and from the manufacture of fertilizers and refined oil products. 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. 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 essentially unlimited source of carbon.Contacting the carboxylic acid with hydrogen to form a reaction product may be performed in (a final step). In preferred implementations, the reaction product includes one or more of formaldehyde, methanol, glycolic acid, glyoxal, glyoxylic acid, glycolaldehyde, ethylene glycol, acetic acid, acetaldehyde, ethanol, propylene glycol, or isopropanol."
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We've abbreviated our excerpts for the sake of concision; and, the full process is a bit more complex than the above might make it seem.
And, although some Hydrogen is made available within the process, as via our inserted comment and reference concerning "water oxidation", additional Hydrogen seems required for reaction with the intermediate reaction product or products, i.e., "carboxylic acid", in order to synthesize the desired end products, i.e., "methanol, ... ethanol", etc.
To that end, we remind you that, as seen for one example in our report of:
West Virginia Coal Association | California Thermochemical Hydrogen Production | Research & Development; concerning: "United States Patent 7,960,063 - Hydrogen Production by a Thermochemical Water Splitting Cycle; 2011; Assignee: The Regents of the University of California; Abstract: A novel thermochemical cycle for the decomposition of water is presented. Along with water, hydrogen, and oxygen, the cycle involves an alkali or alkali earth metal based process intermediate and a variety of reaction intermediates. The cycle is driven by renewable energy sources, and can have a maximum operating temperature below 1173 K (900 C). The kinetics of the cycle are based on the reactant behavior as well as the separability characteristics of the chemicals involved";
we're getting pretty sophisticated in our ability to extract Hydrogen from Water, H2O, in processes that, if you read the full report and formal Disclosure of the above "United States Patent 7,960,063 - Hydrogen Production by a Thermochemical Water Splitting Cycle", can not only be initiated by thermal energy which can be derived from environmental sources, but, which processes then generate heat energy which can be exported from the reaction sequence for use elsewhere, thus reducing dramatically the net energy input needed to produce Hydrogen from Water.
Finally, in our excerpts from our subject, "United States Patent 8,592,633 - Reduction of CO2 to Carboxylic Acids, Glycols and Carboxylates", we emphasized the potential for ultimately producing alcohols, i.e., "methanol" and "ethanol" from Carbon Dioxide, since those alcohols can not only be used as fuels, but, since they can also, through known processes that we've many times referenced, be converted rather directly into Gasoline, which is a hot item, so to speak.
But, note that compounds like "ethylene glycol" and "propylene glycol" can also be synthesized from Carbon Dioxide; and, as can be learned via:
Ethylene glycol - Wikipedia, the free encyclopedia; "Ethylene glycol ... is an organic compoundprimarily used as a raw material in the manufacture of polyester fibers and fabric industry, and polyethylene terephthalate resins (PET) used in bottling"; and:
Propylene Glycol - Plastics resins; "Propylene glycol is an important intermediate and raw material in the production of high performance, unsaturated polyester resins (UPR) for uses such as reinforced plastic laminates for marine construction. Propylene glycol works also as reactive element (starter) to produce basic materials (polyols) for the manufacturing of polyurethanes used as rigid or flexible foams, for example, in the insulation and furniture industries";
those compounds are essential raw materials for the manufacture of various high-performance plastics and polymers that are produced in almost vast quantities around the world for use in a multitude of applications; and, in which applications the Carbon Dioxide originally consumed by the process of our subject herein, "United States Patent 8,592,633 - Reduction of CO2 to Carboxylic Acids, Glycols and Carboxylates", in the synthesis of compounds required for the further synthesis of "ethylene glycol" and "propylene glycol", would be forever - - permanently, productively, and profitably - - "sequestered".