United States Patent Application: 0130134049
Our apologies to our readers: Our headline is only peripherally related to the technical core of our dispatch.
And, our apologies to the company who now prefer to be known as "BP".
But, although the geographic and technical scope of their enterprises might have broadened over the years, "British Petroleum" is how some of us geezers came to know, and still remember them, as.
The important thing is this:
BP have acknowledged the feasibility of utilizing Carbon Dioxide, as is co-produced in only a small way, relative to some all-natural and un-taxable, and sometimes capricious, sources of it's 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, for what it truly is:
CO2 is a freely and universally available carbon-containing raw material from which we can, in some cases using environmental energies to drive the processes, synthesize familiar types of hydrocarbon fuels, and organic chemicals of industrial and commercial significance, including plastics and polymers.
First, we remind you of the Princeton University commercial "spin-off", Liquid Light, Inc., of New Jersey, who were formed to reduce the CO2-recycling technologies developed in the Princeton labs of Professor Andrew Bocarsly to practice, and, to further the science of CO2 recycling.
Among their CO2 utilization achievements have been those seen, for a few examples, in our reports of:
West Virginia Coal Association | New Jersey Converts More CO2 into "Valuable Products" | Research & Development; concerning: "US Patent Application 20120132537 - Heterocycle Catalyzed Carbonylation and Hydroformylation with CO2; May 31, 2012; Inventors: Narayanappa Sivasankar, et. al., (Presumed Assignee of rights: Liquid Light, Inc., NJ); Abstract: Methods and systems for heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide are disclosed"; and:
West Virginia Coal Association | New Jersey Improves CO2 Recycling Technology | Research & Development; concerning, in part: "United States Patent Application 0130116474 - Electrochemical Co-Production of a Glycol and an Alkene Employing Recycled Halide; May 9, 2013; Inventors: Kyle Teamey, et. al., DC, FL and 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. Claims: A method for co-producing a first product and a second product, the method comprising the steps of: applying an electrical potential between a cathode of a first region of a first electrochemical cell, including a catholyte comprising carbon dioxide, and an anode of a second region of a first electrochemical cell, the second region including an anolyte (as specified, and) applying an electrical potential between a cathode of a first region of a second electrochemical cell, including a catholyte comprising the carboxylic acid, and an anode of a second region of a 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".Those excerpts are as about as clear as mud, we know, but a reading of the full reports, and of our others concerning Liquid Light, is recommended. They have developed a complete technical system for the electrochemical recycling and conversion of Carbon Dioxide, with the end products being a range of valuable organic chemical products, including high-energy density fuel alcohols, such as Butanol, which can serve as an almost direct replacement for Gasoline.
We're including another of Liquid Light's technical expositions herein; but, that's not really the news.
As per our headline, BP have recognized the value of Liquid Light's CO2 utilization technologies, have begun to invest in them, and are putting their considerable heft behind a push to begin reducing those CO2 utilization technologies to commercial industrial practice.
The following links and excerpts should provide some indication of what's going on:
BP Alternative Energy - Liquid Light; "BP Alternative Energy comprises BP's lower carbon businesses and future growth options outside oil and gas. BP has invested in Liquid Light, an early-stage start-up founded on discoveries in the fields of catalysis from the research lab of Professor Andrew Bocarsly at Princeton University. The technology will allow transportation fuels and industrial chemicals to be made from CO2 using clean, domestic sources of energy, including solar, wind, hydroelectric ... . The company is developing highly-efficient catalysts and chemical processes for converting carbon dioxide to industrial chemicals and fuels using no biological feedstocks. Energy security, reductions in oil imports, and fewer greenhouse gas emissions could be achieved without major changes to existing infrastructure. Liquid Light's technology is a spin-out from Princeton University".:
http://llchemical.com/about/
And, since it's noted that Liquid Light is a company created to commercialize CO2-recycling technologies first emerging "from the research lab of Professor Andrew Bocarsly at Princeton University", following is an example of one of those technologies, as in our report of:
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;
Date: November 20, 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";
wherein it's explained, that, not only did our US Government finance the initial development of the CO2-recycling technology, but, as can be learned in the full Disclosure, fuel alcohol Ethanol is one of the "organic products" which can be synthesized from Carbon Dioxide.
And, herein we see yet another of the CO2 utilization processes being further developed by Light Light, which we presume to be among those BP, aka British Petroleum, intends helping Liquid Light to commercialize.
Comment follows excerpts from the initial link in this dispatch to:
"United States Patent Application 20130134049 - Method and System for the Electrochemical Co-Production of Halogen and Carbon Monoxide for Carbonylated Products.
Date: May 30, 2013
Inventors: Kyle Teamey, et. al., DC, FL and TX
Assignee: Liquid Light, Inc., NJ
Abstract: The present disclosure is a system and method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode. The method may include a step of contacting the first region with a catholyte including carbon dioxide and contacting the second region with an anolyte including a recycled reactant. The method may further include applying an electrical potential between the anode and the cathode sufficient to produce carbon monoxide recoverable from the first region and a halogen recoverable from the second region.
(Note that this is not the first process for the electrolytic chemical reduction of a Carbon Dioxide solution, to form Carbon Monoxide, we have reported to you. As seen for one example in our report of:
West Virginia Coal Association | Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development; concerning: "US Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes; 1987; Assignee: The Standard Oil Company, Cleveland; Abstract: A process for the electrocatalytic reduction of carbon dioxide comprises immersing a transition metal complex with square planar geometry into an aqueous or nonaqueous solution which has been acidified to a (specified) hydrogen ion concentration ... , adding the carbon dioxide, applying an electrical potential of from about -0.8 volts to about -1.5 volts ... , and reducing the carbon dioxide to carbon monoxide";
the concept and technology might have initially been developed by the petroleum industry itself, since, as seen in:
West Virginia Coal Association | Standard Oil Carbon Monoxide + Water = Gasoline | Research & Development; concerning: "United States Patent 4,559,363 - Process for Reacting Carbon Monoxide and Water; 1985; Abstract: A process for reacting carbon monoxide and water in the presence of a cadmium-containing catalyst is disclosed. Claims: A method for the production of hydrocarbons by reacting carbon monoxide and water ... . This invention relates generally to the reaction between carbon monoxide and water, and more particularly concerns such reaction in the presence of a cadmium-containing catalyst. It is a general object of the present invention to provide a method for the direct production of gasoline";
once we have the reactive Carbon Monoxide, as efficiently electrolyzed from Carbon Dioxide, we can do some modestly entertaining and productive things with it.)
Claims: A method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode, the method comprising the steps of: contacting the first region with a catholyte comprising carbon dioxide; contacting the second region with an anolyte comprising a recycled reactant; and applying an electrical potential between the anode and the cathode sufficient to produce carbon monoxide recoverable from the first region and a halogen recoverable from the second region. (and) wherein the recycled reactant is HX, where X is selected from a group consisting of F, Cl, Br, I and mixtures thereof.
The method ... further comprising: reacting the carbon monoxide recovered from the first region, the halogen recovered from the second region and an additional reactant to form a third product and the recycled reactant (and) wherein the additional reactant includes at least one of an amine ... or at least one of an alcohol, methanol, and ethanol, and mixtures thereof.The method ... wherein the third product includes an at least one of isocyanate, methyl isocyanate, butyl isocyanate, ... toluene-diisocyanate, meta-tetramethylxylylene-diisocyanate, (etc.)
(The fact that a variety of "isocyanate"s can, as herein, be synthesized from Carbon Dioxide might be of special interest. As seen, for two examples, in our reports of: .
West Virginia Coal Association | Bayer Corporation Promotes Carbon Dioxide Recycling | Research & Development; concerning the Bayer Corporation brochure: "Three atoms for a clean future; CO2 destined to become a valuable raw material for innovative substances"; wherein Bayer discloses more about their technology for using Carbon Dioxide for the synthesis of "polyol, one of the two building blocks needed to produce polyurethane"; and:
West Virginia Coal Association | Bayer Is Converting Coal Power Plant CO2 Into Plastics | Research & Development; concerning: "Bayer Material Science CO2-to-Plastics Pilot Plant, Germany; In February 2011, Bayer MaterialScience started a new pilot plant (in the) North Rhine-Westphalia state of Germany for producing plastics from carbon dioxide (CO2). It will be used to develop polyurethanes from the waste gas released during power generation. Bayer aims to use CO2 as an alternative to production of polymer materials from fossil fuels. ... The CO2 thus acts as a substitute for the petroleum production of plastics. Polyurethanes are used to produce a wide range of everyday applications. When they are used for the insulation of buildings, the polyurethane saves about 80% more energy than it consumes during production. Light weight polymers are used in the automotive industry, upholstered furniture and mattress manufacturing.Polyurethanes are formed by reacting two monomer units of isocyanates (polymerics isocyanate or diisocyanates) and polyols. The reaction takes place in the presence of specific quantities of catalyst and additives under predetermined conditions. The waste carbon dioxide gas is recycled and used as a raw material in the pilot plant. It produces polyether polycarbonate polyols (PPPs), the chemical precursor which is processed into polyurethanes";Bayer Corporation has established a technology, and is operating a pilot plant in Germany, that consumes Carbon Dioxide in the synthesis of "polyether polycarbonate polyols", which can then be reacted with "isocyantes", as can be produced by the process of our subject herein, "United States Patent Application 20130134049 - Method and System for the Electrochemical Co-Production of Halogen and Carbon Monoxide for Carbonylated Products", also from Carbon Dioxide, to form "polyurethanes", which are immensely valuable polymers with a wide variety of physical properties and a multitude of productive, commercial uses, wherein the CO2 consumed in the syntheses of both the polyol and the isocyanate would remain forever, and productively, "sequestered".)
The method ... further comprising: reacting the halogen recovered from the second region and an additional reactant to form a third product and the recycled reactant (and) wherein the additional reactant is a halocarbon and the third product is a dihalogenated hydrocarbon (and) further comprising: converting the dihalogenated hydrocarbon to acetylene and the recycled reactant via a dehydrohalogenation reaction.
(So, "acetylene" is another of the products which can be made herein from Carbon Dioxide; and, as Liquid Light goes on to disclose, the acetylene can then be further processed for the synthesis of even additional polymer materials. And, Liquid Light goes on to disclose additional routes for the synthesis of isocyantes from Carbon Dioxide.)
Background and Field: The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical co-production of halogen and carbon monoxide for use in carbonylation reactions.
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.
Summary: The present disclosure is directed to a system and method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode. The method may include a step of contacting the first region with a catholyte including carbon dioxide and contacting the second region with an anolyte including a recycled reactant. The method may further include applying an electrical potential between the anode and the cathode sufficient to produce carbon monoxide recoverable from the first region and a halogen recoverable from the second region
(Systems) and methods of electrochemical co-production of products are disclosed. It is contemplated that the electrochemical co-production of products may include a production of a first product, such as reduction of carbon dioxide to carbon monoxide, at a cathode side of an electrochemical cell with co-production of a second product, such as a halogen, at the anode of the electrochemical cell.
Additionally, the present disclosure is directed to a system and method employing an electrochemical cell to to produce a first product and a second product as intermediate products in the production of an isocyanate. Advantageously, in one embodiment, system and method employing an electrochemical cell may produce an isocyanate without intermediate formation of phosgene.
(The above is rather important, actually. Our understanding from other sources is that "phosgene", an immensely toxic and hazardous compound, related to mustard gas, is often an intermediate in the production of isocyanates in at least some currently practiced industrial processes. The production of phosgene, and the hazards it presents, are avoided by this CO2-based technical concept.)
The present disclosure is further directed to production of an additional product, such as isocyanate or alkyl carbonate, via a further reacting the co-products produced via an electrochemical cell, such as carbon monoxide and a halogen, with an additional reactant."
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The Disclosure reveals, as excerpted and highlighted above in the full text, that the "additional reactant", with which the Carbon Monoxide extracted from Carbon Dioxide is combined, could be an "alcohol" such as "methanol" or "ethanol", and, we remind you of our above-cited report concerning "US Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products", wherein "ethanol" is, in the full Disclosure, specified to be one of the products which can, as well, be synthesized from Carbon Dioxide.
Further, as can be learned in our report of:.
West Virginia Coal Association | Sweden Makes Public Report of CO2 to Motor Fuel Recycling | Research & Development; concerning the Swedish newspaper article: "'Iceland As A Green Saudi Arabia'; March 12, 2013; Recently, they shipped the first load to oil company Argos in Holland, for low level blending in gasoline Vulcanol is just a name for methanol, regular wood spirit. It is the production method which makes this fuel especially interesting. It is made using renewable electricity, water and captured CO2";at least one company, Carbon Recycling International, is, in Europe, already making Methanol from CO2.
So, through the use of Ethanol and/or Methanol as co-reactants for the Carbon Monoxide extracted, via the process of our subject, "US Patent Application 20130134049 - Method and System for the Electrochemical Co-Production of Halogen and Carbon Monoxide for Carbonylated Products", from Carbon Dioxide, the potentials for consuming Carbon Dioxide, as recovered from whatever handy source, in the synthesis of polymer materials, is even further extended and increased, and the need for OPEC imports is even further reduced.
We, here, simply aren't, for a number of reasons, able to fully and accurately explain for you all of the technical details embodied in "United States Patent Application 20130134049 - Method and System for the Electrochemical Co-Production of Halogen and Carbon Monoxide for Carbonylated Products".
In sum, it discloses a method whereby Carbon Dioxide, as recovered from whatever source, can be efficiently converted, through intermediate and integral production of Carbon Monoxide, into, at least, one product, "isocyanate", which serves as half of a formulation, with the other half, a "polyol", also capable of being synthesized from Carbon Dioxide as per our citations of the Bayer Corporation technologies, and, which formulation reacts to form polyurethane, a polymeric material of immense worldwide importance, utility and commercial value.
And, again, there is so much potential value in the Carbon Dioxide utilization processes being developed, as herein, by the Princeton University "spin off", Liquid Light, that a major global petroleum producer, BP, has become invested in the company and the technology.
And, given the potential importance of Carbon Dioxide emission regulations, including Carbon taxation, on United States Coal Country, aren't such Carbon Dioxide utilization processes something in which we all should become at least a little bit interested?