United States Patent Application: 0120171583
We've documented many times that the potential exists for what is, essentially, the electrolysis of Carbon Dioxide, or co-electrolysis of CO2 with a co-reactant, usually H2O, a process sometimes referred to as "syntrolysis", in order to chemically reduce or recombine Carbon Dioxide, and/or it's co-reactants, into more active chemical species.
An early example of such technology was developed at one of our US National Laboratories, as seen in:
West Virginia Coal Association | USDOE 1976 Atmospheric CO2 to Methanol | Research & Development; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Assignee: The USA as represented by the USDOE; Abstract: A method and system for synthesizing methanol from the CO2 in air using electric power. The CO2 is absorbed by a solution of KOH to form K2CO3 which is electrolyzed to produce methanol, a liquid hydrocarbon fuel".
Such reactions take quite a bit of energy, electrical power, to drive them forward; and, efforts were subsequently made to, one way or another, reduce the power demand; as seen, for one example, in:
West Virginia Coal Association | Texaco Recycles More CO2 to Methanol and Methane | Research & Development; concerning: "United States Patent 4,609,451 - Means for Reducing Carbon Dioxide to Provide a Product; 1986; Assignee: Texaco Incorporated; Abstract: A process and apparatus for reducing carbon dioxide to at least one useful product includes two redox couple electrolyte solutions separated by a first membrane having photosensitizers. The carbon dioxide to be reduced is provided to a second membrane whch is contiguous to one of the redox couple electrolyte solutions. The second membrane has photosensitizers and a catalyst. Water provides hydrogen ions, which participate in the reduction of the carbon dioxide, via a separator. In operation both membranes are illuminated and produce excited photosensitizers which cause electron transfer from a first redox solution to a second redox solution and thence to the carbon dioxide in the second membrane thereby, in cooperation with the hydrogen ions, reducing at least some of the carbon dioxide at a surface of the second membrane to provide at least one product. The present invention relates to photoelectrical chemical methods and apparatus for reducing carbon dioxide ... to at least one useful product (which) includes two redox couple electrolyte solutions separated by a first membrane having photosensitizers. The carbon dioxide to be reduced is provided to a second membrane which is contiguous to one of the redox couple electrolyte solutions. The second membrane has photosensitizers and a catalyst";
wherein light energy and "a catalyst" are employed to reduce the electric potential needed to chemically reduce Carbon Dioxide and drive it's recombination with other reactants.
Thermal energy, too, can be employed for that purpose, as also demonstrated by the USDOE, and their corporate partners, as seen for one example in:
West Virginia Coal Association | More USDOE CO2 "Syntrolysis" | Research & Development; concerning:
"Co-Electrolysis of Steam and Carbon Dioxide for Production of Syngas; 2007; Idaho National Laboratory, USDOE; and Ceramatec, Inc., Utah; Abstract: An experimental study has been completed to assess the performance of single-oxide electrolysis cells ... simultaneously electrolyzing steam and carbon dioxide for the direct production of syngas. Syngas, a mixture of hydrogen and carbon monoxide, can be used for the production of synthetic liquid fuels via Fischer-Tropsch processes";
wherein H2O is first converted into Steam; and, the Steam and the CO2 are then "co-electrolyzed".
We've previously reported that rather extensive developments in such energized and catalyzed processes for the co-conversion of CO2 and H2O have also been established at the Princeton University labs of Professor Andrew Bocarsly, as seen, for instance, in:
West Virginia Coal Association | Princeton Recycles CO2 with US Government Support | Research & Development; concerning: "US Patent Application 20100187123A1 - Conversion of Carbon Dioxide to Organic Products; 2010; Inventors: Andrew B. Bocarsly and Emily Barton Cole, NJ; Government Interests: This invention was made with United States government support from Natural Science Foundation Grant No. CHE-0606475. The United States Government has certain rights in this invention. 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 (with) a catalyst of one or more substituted or unsubstituted aromatic amines to produce therein a reduced organic product. Claims: A method of converting of carbon dioxide to provide at least one product, comprising reducing the carbon dioxide in a divided electrochemical cell ... . (And) wherein the reducing is electrochemical or photoelectrochemical (and) where the at least one product is methanol, isopropanol, formic acid, formaldehyde, glyoxal or ethanol".
And, note that, as we explained more fully in our report of:
West Virginia Coal Association | Princeton Scientists Convert More CO2 to Methanol and Ethanol | Research & Development; concerning: "United States Patent Application 20110114502 - Reducing Carbon Dioxide to Products; 2011; Inventors: Emily Barton Cole (and) Andrew Bocarsly, et. al., NJ, DC and CA";
Princeton scientists Bocarsly and Cole have joined forces with other like-mined scholars to form the company, "Liquid Light", as explained via:
Liquid Light :: About; "Liquid Light is uniquely developing a low-cost, energy-efficient system to convert CO2 into a wide variety of chemicals and liquid fuels using clean energy sources. Through its patent-pending catalytic platform originated from the renowned research lab of Professor Andrew Bocarsly at Princeton University, the Company’s carbon conversion approach incorporates low-cost inputs with long-term pricing predictability, reduces capital expenditures by going direct from CO2 to the final product, achieves energy efficiency through its particular catalysts, and offers selective conversion to a desired end product. Additionally, its process leverages secure, clean, domestic sources of energy with reduced emissions, and can store intermittent clean energy as liquid fuels. The Company is based in New Jersey with a core team from the likes of DARPA and the labs of the DOE, Berkeley, and Princeton. They are supported by leading experts in the fields of catalysis and carbon dioxide utilization".
And, herein, we learn that Princeton's Andrew Bocarsly and a few of his other colleagues, have "merged" some of the prior art Carbon Dioxide chemical reduction and conversion technology, as outlined in general by our references to prior reports, and recently applied for a United States Patent on what we see as something of a consolidated technology for recycling CO2.
As seen, with notes and comment inserted and appended, in excerpts from the initial link in this dispatch to:
"United States Patent Application 20120171583 - Gas Phase Electrochemical Reduction of Carbon Dioxide
(GAS PHASE ELECTROCHEMICAL REDUCTION OF CARBON DIOXIDE - LIQUID LIGHT, INC.)
Date: July 5, 2012
Inventors: Andrew Bocarsly, et. el., NJ and IL
Assignee: Liquid Light, Inc., NJ
Abstract: Methods and systems for gas phase electrochemical reduction of carbon dioxide are disclosed. A method for gas phase electrochemical reduction of carbon dioxide may include, but is not limited to, steps (A) to (C). Step (A) may include introducing a substantially gas phase fuel to an anode flow field of an anode of a proton exchange membrane (PEM) fuel cell. Said anode may be a gas diffusion electrode. Step (B) may include introducing a substantially gas phase carbon dioxide to a cathode flow field of a cathode of said PEM fuel cell. Said cathode may be a chemically modified gas diffusion electrode including a coating of a polymer aromatic amine. Step (C) may include reducing at least a portion of said substantially gas phase carbon dioxide to a product mixture at said cathode.
(Note the term "fuel cell". A number of emerging CO2 recycling technologies seem to spring from the concept of running a fuel cell "in reverse", so to speak, using Carbon-free environmental energy to drive the processes. Another example of such "reverse fuel cell" technology is seen in our report concerning the USDOE's "syntrolysis" partner, as in our above-cited report concerning "Co-Electrolysis of Steam and Carbon Dioxide for Production of Syngas", the Utah company, Ceramatec:
West Virginia Coal Association | Utah 2011 CO2 + H2O = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; Date: December 13, 2011; Assignee: Ceramatec, Inc., Salt Lake City; Abstract: A method is provided for synthesizing synthesis gas from carbon dioxide obtained from atmospheric air or other available carbon dioxide source and water using a sodium-conducting electrochemical cell. Synthesis gas is also produced by the coelectrolysis of carbon dioxide and steam in a solid oxide fuel cell or solid oxide electrolytic cell. The synthesis gas produced may then be further processed and eventually converted into a liquid fuel suitable for transportation or other applications".
Also, concerning the specified "gas diffusion electrode", see:
Gas diffusion electrode - Wikipedia, the free encyclopedia.)
Claims: A method for gas phase electrochemical reduction of carbon dioxide, comprising:
(A) introducing a substantially gas phase fuel to an anode flow field of an anode of a proton exchange membrane (PEM) fuel cell, wherein said anode is a gas diffusion electrode;
(Proton exchange membrane fuel cell - Wikipedia, the free encyclopedia; "Proton exchange membrane fuel cells, also known as polymer electrolyte membrane (PEM) fuel cells (PEMFC), are a type of fuel cell being developed for transport applications as well as for stationary fuel cell applications and portable fuel cell applications. Their distinguishing features include lower temperature/pressure ranges (50 to 100 °C) and a special polymer electrolyte membrane. They are a leading candidate to replace the aging alkaline fuel cell technology, which was used in the Space Shuttle.")
(B) introducing a substantially gas phase carbon dioxide to a cathode flow field of a cathode of said PEM fuel cell, wherein said cathode is a chemically modified gas diffusion electrode including a coating of a polymer aromatic amine; and;
(C) reducing at least a portion of said substantially gas phase carbon dioxide to a product mixture at said cathode.
The method ... where said coating of said polymer aromatic amine comprises a coating of a pyridinium-containing polymer.
(Pyridinium - Wikipedia, the free encyclopedia; "Pyridinium refers to (a) form of pyridine."
Pyridine - Wikipedia, the free encyclopedia; "Pyridine is a basic heterocyclic organic compound ... structurally related to benzene ... (and) occurs in many important compounds, including ... the vitamins niacin and pyridoxal. Pyridine was discovered in 1849."
It is, in other words, easy to get.)
The method ... wherein introducing a substantially gas phase fuel to an anode flow field of an anode of a proton exchange membrane (PEM) fuel cell comprises: introducing a humidified hydrogen stream to said anode flow field of said anode of said PEM fuel cell.
(If we need Hydrogen, there are many ways to efficiently get some, as we documented most recently in:
West Virginia Coal Association | Japan Maximizes Hydrogen Production from Wind Power | Research & Development; concerning: "United States Patent 7,667,343 - Hydrogen Production System Using Wind Turbine Generator; 2010; Assignee: Hitachi, Ltd.; A wind turbine-driven hydrogen production system".
However, the reverse fuel cell "syntrolysis"-type technology employed by the Idaho National Lab and Ceramatec, as per our above-cited references, apparently doesn't require Hydrogen supplementation; it's all derived from the H2O being co-reacted with the CO2. Adding Hydrogen as a supplement might improve the efficiency of the process.)
The method ... wherein introducing a substantially gas phase carbon dioxide to a cathode flow field of a cathode of said PEM fuel cell comprises: introducing a humidified carbon dioxide stream to said cathode flow field of said cathode of said PEM fuel cell.
(The qualifier "humidified" means, of course, that it's mixed with H2O.)
The method ... wherein at least one of said gas diffusion electrode of said anode or said chemically modified gas diffusion electrode of said cathode includes a metal nanoparticle on carbon gas diffusion electrode.
The method ... wherein said product mixture includes at least one of methanol or propanol.
The method ... wherein said PEM fuel cell provides between approximately 30% to 95% faradaic yield for methanol.
(The phrase "faradaic yield" equates with: Faraday efficiency - Wikipedia, the free encyclopedia. And, "95%" is pretty darned good.)
A system for gas phase electrochemical reduction of carbon dioxide, comprising: a fuel cell, including: an anode including a gas diffusion electrode having an anode flow field; a cathode including a chemically modified gas diffusion electrode having a coating of a polymer aromatic amine; and a membrane electrode assembly positioned between said anode and said cathode; a fuel source, said fuel source coupled with said anode, said fuel source configured to supply a gaseous fuel to said anode flow field; and a carbon dioxide input, said carbon dioxide input configured to be coupled between a carbon dioxide source and said cathode, said carbon dioxide input configured to provide gaseous carbon dioxide to said cathode flow field for reduction of said gaseous carbon dioxide to a product mixture at said cathode.
The system ... wherein said gaseous fuel includes humidified hydrogen.
(Again, if we need supplemental Hydrogen, as seen for another example in:
More NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,051,005 - Photolytic Production of Hydrogen; 1977; Assignee: United Technologies Corporation;
Government Interests: The invention described herein was made in the course of a contract with the National Aeronautics and Space Administration. Abstract: Hydrogen and oxygen are produced from water in a process involving the photo-dissociation of molecular bromine with radiant energy at wavelengths within the visible light region";
we can get it through the use of environmental energies, in ways that shouldn't break the bank.)
Background and Field: The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for gas phase electrochemical reduction of carbon dioxide.
Countries around the world, including the United States, are seeking ways to mitigate emissions of carbon dioxide.
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.
However, the field of electrochemical techniques in carbon dioxide reduction has many limitations, including the stability of systems used in the process, the efficiency of systems, the selectivity of the systems or processes for a desired chemical, the cost of materials used in systems/processes, the ability to control the processes effectively, and the rate at which carbon dioxide is converted. In particular, existing electrochemical and photochemical processes/systems have one or more of the following problems that prevent commercialization on a large scale. Several processes utilize metals, such as ruthenium or gold, that are rare and expensive. In other processes, organic solvents were used that made scaling the process difficult because of the costs and availability of the solvents, such as dimethyl sulfoxide, acetonitrile, and propylene carbonate. Copper, silver and gold have been found to reduce carbon dioxide to various products, however, the electrodes are quickly "poisoned" by undesirable reactions on the electrode and often cease to work in less than an hour. Similarly, gallium-based semiconductors reduce carbon dioxide, but rapidly dissolve in water. Many cathodes produce a mixture of organic products. For instance, copper produces a mixture of gases and liquids including carbon monoxide, methane, formic acid, ethylene, and ethanol. Such mixtures of products make extraction and purification of the products costly and can result in undesirable waste products that must be disposed. Much of the work done to date on carbon dioxide reduction is inefficient because of high electrical potentials utilized, low faradaic yields of desired products, and/or high pressure operation. The energy consumed for reducing carbon dioxide thus becomes prohibitive. Many conventional carbon dioxide reduction techniques have very low rates of reaction.
Summary and Description: A method for gas phase electrochemical reduction of carbon dioxide may include, but is not limited to, steps (A) to (C). Step (A) may include introducing a substantially gas phase fuel to an anode flow field of an anode of a proton exchange membrane (PEM) fuel cell. Said anode may be a gas diffusion electrode. Step (B) may include introducing a substantially gas phase carbon dioxide to a cathode flow field of a cathode of said PEM fuel cell. Said cathode may be a chemically modified gas diffusion electrode including a coating of a polymer aromatic amine. Step (C) may include is reducing at least a portion of said substantially gas phase carbon dioxide to a product mixture at said cathode.
The system may further include a carbon dioxide input. Said carbon dioxide input may be coupled between a carbon dioxide source and said cathode and may be configured to supply gaseous carbon dioxide to said cathode flow field for reduction of said gaseous carbon dioxide to a product mixture at said cathode.
(An) electrochemical system is provided that generally allows electrochemical reduction of carbon dioxide substantially in the gas phase, thereby utilizing the greenhouse gas as a reactant to transfer the reaction energy into a chemical form that can be stored for later use.
By facilitating the electrochemical reduction of carbon dioxide in the gas phase, improved reaction rates (e.g., as measured by current density of the electrochemical cell) may be achieved as compared to the reaction rate of a liquid-based electrochemical system."
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And, don't forget, the "product mixture" obtained at up "to 95% faradaic yield", from recycled Carbon Dioxide, "includes at least one of methanol or propanol".
Methanol, as seen in:
Mobil Oil Coal to Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline; 1984; Assignee: Mobil Oil Corporation;
Abstract: A process for producing a wide slate of fuel products from coal is provided by integrating a methanol-to-gasoline conversion process with coal liquefaction and coal gasification. The coal liquefaction comprises contacting the coal with a solvent under supercritical conditions whereby a dense-gas phase solvent extracts from the coal a hydrogen-rich extract which can be upgraded to produce a distillate stream. The remaining coal is gasified under oxidation conditions to produce a synthesis gas which is converted to methanol. The methanol is converted to gasoline by contact with a zeolite catalyst. Solvent for coal extraction is process derived from the upgraded distillate fraction or gasoline fraction of the methanol-to-gasoline conversion";
no matter which of our abundant resources, Carbon Dioxide, as herein, or Coal, we make it from, can be efficiently converted into Gasoline.
On the other hand, as seen in:
chemical industry : Ethanol and its products -- Britannica Online Encyclopedia; "The alcohol 2-propanol ... is manufactured on the million-ton scale. It is made from propylene by a process similar to that used to convert ethylene to ethanol, and manufacture of 2-propanol by this process initiated the petrochemical industry in the 1920s. The principal use of 2-propanol is in the manufacture of acetone, which is used extensively as a solvent and as a starting material in the manufacture of numerous other organic compounds";
and, in:
Acetone - Wikipedia, the free encyclopedia; "(One) major use of acetone ... is synthesizing bisphenol A. Bisphenol A is a component of many polymers such as polycarbonates, polyurethanes and epoxy resins";
the "propanol" can be used and consumed in the synthesis of a number of valuable plastics and polymers, which we now rely pretty much on raw materials from OPEC to manufacture; plastics and polymers wherein the Carbon Dioxide, consumed by the process of our subject herein, "United States Patent Application 20120171583 - Gas Phase Electrochemical Reduction of Carbon Dioxide", to synthesize the "propanol", would be permanently, and profitably and productively, "sequestered".
The Carbon Dioxide recycling technology disclosed by Princeton scientist Andrew Bocarsly, and his Princeton and Liquid Light colleagues, is similar to, but apparently more efficient than, others, similar, we have brought to your attention; and, one key factor seems to lie in it's "gas phase" processing.
However, this same core team has developed other, related, CO2-recycling processes, as well, as we will further document in reports to follow.
And, they all point to one conclusion:
Carbon Dioxide, as it arises in only a small way, relative to natural sources of emission, such as volcanoes, from our essential use of Coal in the generation of truly economical electric power, is a valuable raw material resource.
As seen in the Disclosure of our subject, "United States Patent Application 20120171583", we can efficiently convert Carbon Dioxide into basic alcohols; and, from those alcohols, Methanol and Propanol, we can, through other established technologies, manufacture both various plastics and, even, Gasoline; things we now squander our national treasure to acquire from the often inimical nations of OPEC.
Why, in the world, would we ever want to even consider squandering such a valuable resource as CO2 in specious scams like the mandated geologic sequestration of CO2 in old oil wells, for the purposes of subsidized secondary petroleum recovery?
Why, in the world, would we want to abuse the producers of such a resource, and their customers, through punitive Cap & Trade taxes?
Time we all woke up, and far past time for some "good news" to be published, ain't it?
