We've documented for you in several reports the development, some of it supported by the US Government, by scientists at New Jersey's Princeton University, of technologies wherein Carbon Dioxide, as reclaimed from whatever handy source, can be converted efficiently into, among other things, fuel alcohols.
Our reports have included, for one example: 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;
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. 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".We've also documented and separately reported that the key Princeton scientists, including the above Bocarsly and Cole, have teamed with other experts to forge a spin-off company, Liquid Light, LLC, to further develop and refine such Carbon Dioxide recycling technologies, as reported by Princeton University via:
Princeton University - Startup born in Princeton lab turns carbon dioxide into fuels; concerning the Princeton University news release: "'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. Liquid Light's core technology involves taking carbon dioxide and mixing it in a water-filled chamber with an electrode and a catalyst to convert carbon dioxide into methanol. 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".More about them can be learned in our report of:
West Virginia Coal Association | Princeton Scientists Convert More CO2 to Methanol and Ethanol | Research & Development; which contains a separate link to:
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 industrial chemicals and fuels".
Further, we've seen that the Princeton spinoff, Liquid Light, has continued to develop Carbon Dioxide recycling technologies founded on the science established in the Bocarsly Labs, as for one example in:
West Virginia Coal Association | New Jersey Improves CO2 Recycling Technology | Research & Development; concerning: "United States Patent Application 20130105304 - High Surface Area Electrodes for the Electrodes for the Electrochemical Reduction of Carbon Dioxide; May 2, 2013; Inventors: Jerry Kaczur, et. al., FL, NY, NJ, and CA; Assignee: Liquid Light, Inc., NJ; Abstract: Methods and systems for electrochemical conversion of carbon dioxide to organic products ... are provided. A system may include an electrochemical cell including a cathode compartment containing a high surface area cathode and a bicarbonate-based catholyte saturated with carbon dioxide. ... The electrochemical cell may be configured to produce a product stream upon application of an electrical potential between the anode and the cathode".
And, herein, via excerpts from the initial link in this dispatch, we see that Liquid Light, with the participation of Princeton University scientists Bocarsly and Cole, have developed and refined technology wherein Carbon Dioxide can be harvested, presumably for use as a raw material in the synthesis of "organic products", such as, perhaps, "ethanol":
"United States Patent 8,500,987 - Purification of Carbon Dioxide from a Mixture of Gases
Purification of carbon dioxide from a mixture of gases - Liquid Light, Inc.
Date: August 6, 2013
Inventors: Kyle Teamey, Emily Barton Cole, Narayanappa Sivasankar, Andrew Bocarsly, DC and NJ
Assignee: Liquid Light, Inc., NJ
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 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 one or more of oxalate, organic acids and oxalate salts and (iii) said anode oxidizing at least one of said one or more of oxalate, organic acids and oxalate salts into said carbon dioxide; (B) separating said carbon dioxide from said solution; and (C) adding to said solution one or more of (i) a hydrogen inhibitor, (ii) a heterocyclic compound and (iii) an alcohol.
The method ... wherein said oxidizing uses at most two electrons per carbon atom (and) wherein said purification consumes approximately no additional water after said solution has been established in said divided electrochemical cell (and) wherein an energy consumed by said purifying of said carbon dioxide is less than 500,000 watt hours per ton of carbon dioxide.
(This could, in other words, be a very energy-efficient way of extracting relatively pure Carbon Dioxide from just about any "mixture of gases".)
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.
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.
Summary: 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 provide for new cathode materials, new electrolyte materials and new sulfur and oxygen-containing heterocyclic catalysts. Specific combinations of cathode materials, electrolytes and catalysts may be used to get a desired organic compounds that may be used to efficiently purify (separate) carbon dioxide from other gases. Specific process conditions may be established that maximize the carbon dioxide conversion to oxalate. The oxalate may be evolved back into carbon dioxide at the anode and/or stored then evolved at a later time. A result may be a purer form of carbon dioxide gas than the original mixed gas.
Cell parameters may be selected to minimize unproductive side reactions like H2 evolution from water electrolysis (and) may facilitate long life (e.g., improved stability), electrode and cell cycling and product recovery.
Some embodiments of the present invention may provide cathode and electrolyte combinations for reducing carbon dioxide to organic compounds in commercial quantities. Catalytic reduction of carbon dioxide may be achieved using various cathodes. High faradaic yields ... of organic compounds with steel and nickel alloy cathodes at ambient temperature and pressure may also be achieved. Copper-based alloys used at the electrodes may remain stabile for long-term reduction of carbon dioxide.
Some embodiments of the present invention may provided for capturing carbon dioxide from a mixture of gases (and, the) purification generally consumes lower amounts of energy, (has) reaction rates high enough for scalability, and remains stable for long periods.
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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We have, of course, not reproduced many of the technical details; we're forced to leave study of those to the more astute who might be among our readers.
One important thing to note, in addition to the efficiency and lower energy consumption, is the element of "scalability"; that is, the process can be built to a size suitable for any given Carbon Dioxide capture application, which leads to "the possibility for commercial systems that are modular and adaptable to different situations".
Further, the design of the thing is such that it "may remain stabile for long-term reduction of carbon dioxide".
It is, basically, a high-efficiency CO2 scrubbing solution, coupled with an efficient, lower-energy method to treat that solution for the efficient extraction, or release, from that solution, of the Carbon Dioxide that has been absorbed.
Which Carbon Dioxide could then be directed to and, if we read the full Disclosure of our subject herein,
"United States Patent 8,500,987 - Purification of Carbon Dioxide from a Mixture of Gases", correctly, made immediately available for, another process developed by the scientists at Liquid Light, as in our report of:
West Virginia Coal Association | New Jersey CO2 to High-Energy Alcohol | Research & Development; concerning: "United States Patent Application: 0120132538 - Electrochemical Production of Butanol from Carbon Dioxide and Water; May, 2012; Inventors: Emily Barton Cole, Kyle Teamey, Andrew Bocarsly, and Narayanappa Sivasankar, NJ and DC; (Presumed eventual Assignee of Rights: Liquid Light); 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";
wherein the efficiently-captured and purified Carbon Dioxide can be used and chemically consumed in the synthesis of a high-energy density alcohol, Butanol, which can itself, unlike Methanol or Ethanol, as we've documented in other of our reports, be used as an almost direct substitute for Gasoline.
Yet again: Carbon Dioxide, as it arises in only a small way, relative to natural sources of emission such as the Earth's inexorable processes of planetary volcanism, from our economically essential use of Coal in the generation of truly abundant and truly affordable electric power, can be seen as a valuable raw material resource. It is a resource which we can, according to the process of our subject herein, "United States Patent 8,500,987 - Purification of Carbon Dioxide from a Mixture of Gases", efficiently reclaim and purify "from a mixture of gases", perhaps "a mixture of gases" arising "from industrial sources, such as a coal-fired power plant", and thus make that Carbon Dioxide directly available for, via the processes of, for example, "United States Patent Application 0120132538 - Electrochemical Production of Butanol from Carbon Dioxide and Water" and "United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products", the subsequent, efficient conversion of that "coal-fired power plant" CO2 into a variety of valuable fuel alcohols.