|New Jersey Converts More CO2 into "Valuable Products"|
|Saturday - July 14, 2012|
United States Patent Application: 0120132537
We return herein to the Carbon Dioxide recycling exploits of a band of accomplished scientists, a group with roots in Princeton University, who have been hard at work in the state of New Jersey to establish not just the technological foundations of a fuels and chemicals manufacturing industry based on CO2 as the primary raw material, but, to reduce those technological foundations to actual commercial, industrial practice.
In several previous reports, including:
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; 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. A method of converting of carbon dioxide to provide at least one product, comprising reducing the carbon dioxide in a divided electrochemical cell ... wherein the reducing is electrochemical or photoelectrochemical ... (and) where the at least one product is methanol, isopropanol, formic acid, formaldehyde, glyoxal or ethanol"; and:
West Virginia Coal Association | New Jersey Recycles More Carbon Dioxide | Research & Development; concerning:
"US Patent Application 20110114504 - Electrochemical Production of Synthesis Gas from Carbon Dioxide; 2011; Inventors: Narayanappa Sivasankar, Emily Barton Cole and Kyle Teamy, NJ and DC; A method for electrochemical production of synthesis gas from carbon dioxide is disclosed"; and:
West Virginia Coal Association | Princeton Scientists Convert More CO2 to Methanol and Ethanol | Research & Development; concerning:
"US Patent Application 20110114502 - Reducing Carbon Dioxide to Products; 2011; Inventors: Emily Barton Cole (and) Andrew Bocarsly, et. al., NJ, DC and CA; A method for reducing carbon dioxide to one or more products is disclosed ... wherein said products (of the Carbon Dioxide chemical reduction) comprise one or more of acetaldehyde, acetone, carbon, carbon monoxide, carbonates, ethanol, ethylene, formaldehyde, formic acid, glyoxal, glyoxylic acid, graphite, isopropanol, methane, methanol, oxalate, oxalic acid and polymers containing carbon dioxide";
we documented how a core Carbon Dioxide recycling technical base, and a CO2 recycling enterprise, "Liquid Light", had arisen in and emerged from the Princeton University labs of Professor Andrew Bocarsly.
For more background, see:
Princeton University - 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 above article goes on to explain how entrepreneur Kyle Teamey became aware of the work and, with Bocarsly's former graduate student, Dr. Emily Barton Cole, and a "team of chemists", founded Liquid Light. It's further reported that the "research has received funding from the Air Force Office of Scientific Research (AFSOR), the National Science Foundation and the Department of Energy"; and, that 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".
Moreover, not only has, as above, the United States Government taken supportive notice of the fact that Liquid Light and Princeton University know how to convert Carbon Dioxide into "industrial chemicals and fuels", but, as in:
BP Alternative Energy - Liquid Light; "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 waste CO2 using clean, domestic sources of energy, including solar, wind (and) 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";
so have some significant "others".
In any case, the Liquid Light team continues to refine and enhance their suite of technologies for the productive recycling of Carbon Dioxide, as seen, with additional comment appended, in excerpts from the initial link in this dispatch to the very recent:
"US Patent Application 20120132537 - Heterocycle Catalyzed Carbonylation and Hydroformylation with CO2
(Since official USPTO links to US Patent Applications, as included above, sometimes do not prove durable, here's a backup:
HETEROCYCLE CATALYZED CARBONYLATION AND HYDROFORMYLATION WITH CARBON DIOXIDE - Sivasankar, Narayanappa.)
Date: May 31, 2012
Inventors: Narayanappa Sivasankar, Emily Barton Cole and Kyle Teamey
(As we've previously reported, the ultimate assignee of rights to United States Patents seem most often not to be named in early published versions of United States patent applications. In this case, the Assignee will almost certainly be Liquid Light. And, again, for more information on Liquid Light, here's a link to their web site, wherein you might find some intriguing information:
Liquid Light; "Liquid Light develops technology for conversion of carbon dioxide to chemicals and fuels. Clean, secure energy."
Further, most of you, as were we, are likely blinded by the title's "Heterocycle Catalyzed Carbonylation and Hydroformylation". Don't despair. As our trusty, nearly-omniscient friend, the Wikipedia, explains, via:
Carbonylation - Wikipedia, the free encyclopedia; "carbonylation" just means that Carbon Monoxide is being chemically attached to other molecules, while "hydroformylation" means that both Carbon Monoxide and Hydrogen are being used as reactants and being thus compounded. That might be a tad bit of an oversimplification; but, until one of our Coal Country journalists behooves themselves to get off their dead cans and consult with someone genuinely knowledgeable about it all, and then harnesses their nebulous skills to explain it all more clearly to the rest of us, that will have to suffice. The full Disclosure, however, does serve to enlighten, just a little; including making clear the fact that the reactants are electrochemically derived from Water and Carbon Dioxide.)
Abstract: Methods and systems for heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide 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 heterocyclic catalyst, and a cathode. Step (C) may introduce a second reactant to the second compartment of the electrochemical cell. Step (D) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient to induce liquid phase carbonylation or hydroformylation to form a product mixture.
(Unfortunately, even the Wikipedia is stumped, as they confess, when it comes to what a "heterocyclic catalyst" might be. However, as seen in:
Heterocycles and Catalysts -> HetCat; "HetCat specialises in customer synthesis of heterocyclic compounds (5-, 6- and 7-membered rings having 1 and/or more N, O, S atoms in molecules), their metal complexes and catalysts";
there are some folks out there who do know about them; and, in fact, there are apparently folks who know enough about them to be using them commercially and other folks who know enough about them to be making them and selling them to those folks who are using them.
The point we're trying to make is, that, even though the materials required aren't as simple as the Iron and Nickel we typically need to catalyze the synthesis of hydrocarbon liquids out of synthesis gas made from Coal, in the Fischer-Tropsch and related technologies, "heterocyclic catalyst"s aren't moon rocks or specks of fairy dust. There are, God bless 'em, technically astute folk out there who know what they are, where to get them, and, as herein, how to use them.)
Claims: A method for hydroformylation with carbon dioxide, comprising: (A) introducing water to a first compartment of an electrochemical cell, said first compartment including an anode; (B) introducing carbon dioxide to a second compartment of said electrochemical cell, said second compartment including a solution of an electrolyte, a heterocyclic catalyst, and a cathode; (C) introducing an alkene to said second compartment of said electrochemical cell; and (D) applying an electrical potential between said anode and said cathode in said electrochemical cell sufficient for said cathode to induce liquid phase hydroformylation to form a product mixture.
(Note, that, in this process, a reaction vessel is structured so that, via the good offices of a "heterocyclic catalyst" and some small amount of "electrical potential", CO2 is made to effect an "hydroformylation" with an unspecified "alkene".
And, as taught by:
Alkene - Wikipedia, the free encyclopedia; "The simplest alkene is ethylene" which, as in the above-cited "US Patent Application 20110114502 - Reducing Carbon Dioxide to Products", is one of the primary products, along with "ethanol", and a few others, being made from CO2 in the first place. The co-product Ethanol, by the way, as in:
http://www.gidynamics.nl/uploads/files/GI_Dynamics_-_Ethanol-to-Ethylene-Technology-Folder.pdf; "The Ethanol to Ethylene technology is a very efficient, safe and commercially proven technology from sustainable and renewable feedstocks for producing a basic chemical which is a building block and heart and soul of modern petrochemical industry, that is otherwise produced via a petroleum route";
can itself be converted into even more ethylene, i.e., more of the "alkene" required by the process of our subject, "US Patent Application 20120132537", to react with even more Carbon Dioxide in order to form the products hereinafter specified. Thus, the process of our subject, in one aspect, is a technology for reacting Carbon Dioxide with various products, which products themselves have been or could be synthesized from Carbon Dioxide in the first place, in order to make other products of even higher value.)
The method ... wherein said product mixture includes at least one of a carboxylic acid, an aldehyde, or an alcohol.
The method ... wherein said solution of said electrolyte includes at least one of potassium chloride or potassium sulfate.
The method ... wherein said second compartment further includes a metal oxide reaction promoter.
The method ... wherein said alkene includes at least one of ethylene, propylene, 1-butylene, 2-butylene, butadiene, an unsaturated alcohol, or an unsaturated organic reactant.
The method ... wherein applying an electrical potential between said anode and said cathode in said electrochemical cell includes: is applying an electrical potential between said anode and said cathode in said electrochemical cell at ambient temperature and pressure.
(In other words, we don't have to spend a lot of money heating or pressurizing the reaction vessels; which vessels, themselves, thus, would be fairly economical to build.)
A method for carbonylation with carbon dioxide, comprising: (A) introducing water to a first compartment of an electrochemical cell, said first compartment including an anode; (B) introducing carbon dioxide to a second compartment of said electrochemical cell, said second compartment including a solution of an electrolyte, a heterocyclic catalyst, and a cathode; (C) introducing at least one of a carboxylic acid, an aldehyde, an alcohol, acetylene, an amine, an aromatic compound, or an epoxide to said second compartment of said electrochemical cell; and (D) applying an electrical potential between said anode and said cathode in said electrochemical cell sufficient for said cathode to induce liquid phase carbonylation to form a product mixture.
The method ... wherein said product mixture includes at least one of an organic acid, an aldehyde, an alcohol, a carbonate, or a cyclic compound.
(Again, we do hate to harp upon our varied disabilities and insufficiencies, but, absent now the services of our former, informal technical advisors, our take on all of this is, that, a sequence of reactions is taking place, or can be made to take place, wherein the products of the first Carbon Dioxide-consuming reaction can be reacted with even more CO2, in a second phase which can produce a different slate of products. Someone genuinely competent needs to make follow up inquiry of Liquid Light themselves.)
The method ... wherein said solution of said electrolyte includes at least one of potassium chloride or potassium sulfate (and) where said heterocyclic catalyst includes at least one of imidazole, pyridine, or a substituted variant of imidazole or pyridine, said substituted variant including at least one of a five member heterocyclic ring or a six member heterocyclic ring.
(Confusing as all get out to us mere mortals, we know; but, we assure you, people educated in appropriate organic chemistry subjects will understand perfectly what is being described.)
A system, comprising: an electrochemical cell including: a first cell compartment; an anode positioned within the first cell compartment; a second cell compartment; a separator interposed between the first cell compartment and the second cell compartment, the first cell compartment and the second cell compartment each containing an electrolyte; and a cathode and a heterocyclic catalyst positioned within the second cell compartment; a carbon dioxide source, the carbon dioxide source coupled with the second cell compartment, the carbon dioxide source configured to supply carbon dioxide to the cathode; a reactant source, the reactant source coupled with the second cell compartment, the reactant source configured to supply at least one of an alkene, a carboxylic acid, an aldehyde, an alcohol, acetylene, an amine, an aromatic compound, or an epoxide to the cathode; a fluid source, the fluid source coupled with the first cell compartment; and an energy source operably coupled with the anode and the cathode, the energy source configured to provide power to the anode and the cathode to induce at least one of hydroformylation or carbonylation at the cathode and to oxidize the fluid at the anode.
Background and Field: The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for heterocycle catalyzed carbonylation and hydroformylation with 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.
Summary: A method for mitigation of carbon dioxide through heterocycle catalyzed hydroformylation using carbon dioxide.
In accordance with some embodiments of the present disclosure, an electrochemical system is provided that generally allows carbon dioxide and water to undergo hydroformylation to produce commercially valuable products under mild process conditions.
In accordance with some embodiments of the present disclosure, an electrochemical system is provided that generally allows carbon dioxide to participate in carbonylation with another reactant to produce commercially valuable products under mild process conditions.
In some embodiments of the present disclosure, the energy used by the systems may be generated from an alternative energy source to avoid generation of additional carbon dioxide through combustion of fossil fuels.
(For some examples and suggestions concerning the above, see our reports of:
West Virginia Coal Association | Hydrogen for Coal and CO2 Conversion from Wind Power | Research & Development; which contains separate documentation of the fact, that: "The U.S. Department of Energy's Wind Program and the National Renewable Energy Laboratory (NREL) published a wind resource map for the state of Pennsylvania. This map indicates that Pennsylvania has ... good-to-excellent wind resource areas ... on ridge crests in the southwestern part of Pennsylvania, located ... southeast of Pittsburgh"; and:
http://hydropower.inl.gov/resourceassessment/pdfs/states/wv.pdf; "U.S. Hydropower Resource Assessment
for West Virginia; 1998; Idaho National Engineering and Environmental Laboratory".)
In general, the embodiments for carbon dioxide to participate as a reactant in hydroformylation and carbonylation do not require syngas as reactants. Some embodiments of the present invention thus relate to environmentally beneficial methods and systems for reducing carbon dioxide, a major greenhouse gas, in the atmosphere thereby leading to the mitigation of global warming. The embodiments provided herein also promote safety by utilizing relatively mild process conditions that do not rely on high pressure/high temperature process conditions. Moreover, certain processes herein are preferred over existing electrochemical processes due to being stable, efficient, having scalable reaction rates, occurring in water, and providing selectivity of desired products."
The document goes on to specify some of the things that can be made by starting out with nothing, essentially, but "carbon dioxide and water", such as "propanol" and "acetone"; but, again in honesty, with our now-reduced cadre of qualified volunteer advisors, much of it is beyond our limited capacities to comfortably attempt explanation.
In coarse sum, our take on it is, that, this is technology which, in a process that consumes very little energy, reacts Carbon Dioxide with other compounds, some of which themselves can be synthesized in similar and related processes from Carbon Dioxide, to synthesize organic products of even greater complexity, and of higher utility and value.
We do note, somewhat regrettably, that the inventors, in the full text of the disclosure, do disqualify Coal power plant exhaust as being well-suited for use in this process, since it contains a number of other contaminants. And, that might be just fine, even though, as we've documented in:
West Virginia Coal Association | Efficient Power Plant CO2 Capture for CO2-to-Fuel Conversion | Research & Development; concerning: "Development of an Economic Post-Combustion Carbon Capture Process; 2008; Siemens develops an improved CO2 capture process with minimized energy demand, optimized for integration in conventional coal-fired power plants";
we think there might actually be some economical ways to recover CO2 of sufficient purity from Coal-fired power plants. But, as we can learn, for just one example, in:
West Virginia Coal Association | California Algae Make Oil from Coal Power Plant Exhaust | Research & Development; concerning, in part: "US Patent Application 20080086938 - Photosynthetic CO2 Sequestration and Pollution Abatement; 2008; Abstract: A system and method for producing biofuel from pollutant-fed algae are disclosed. Specifically, the system includes a scrubber with a chamber for receiving a pollutant-contaminated fluid stream. Further, a scrubber solution is received in the chamber for scrubbing the pollutant-contaminated fluid stream. Also, the system includes a bioreactor that is provided with an input port to receive the scrubber solution with pollutants for use as nutrients to support algae cell growth. Further, the system includes an algae separator that removes the algae from the bioreactor and a device for processing the algae into biofuel. In order to recycle the scrubber solution, the algae separator is in fluid communication with the scrubber. With this arrangement, the effluence from the bioreactor may be recycled for use as the scrubber solution";
it is seems perfectly feasible to consider cultivating Algae with pretty raw Coal power plant exhaust.
And, our read of the various products which can be generated by Algae from flue gas, as specified in the above and in other, related, documents, suggests that Algae could be selected which would recycle the raw flue gas CO2 into some of the intermediate products specified in the process of our subject, "US Patent Application 20120132537 - Heterocycle Catalyzed Carbonylation and Hydroformylation with CO2", which intermediate products could be, at low temperatures and pressures, directed into "Carbonylation and Hydroformylation" reactions with more pure Carbon Dioxide, to form the more highly-valued end products specified herein by the good people at Liquid Light.
We, here, are willing to bet those folks would be happy to clarify all of that for anyone among our Coal Country press who might be somehow motivated enough to give 'em a shout and ask.
In sum, though, it seems clear that we have herein yet another clear statement of the fact that Carbon Dioxide, as it arises in only a very small way, relative to natural sources of emission, such as volcanoes, from our essential use of Coal in the generation of truly economical electrical power, is a raw material resource of potentially great worth.
We can, as disclosed and specified herein, utilize Carbon Dioxide, and consume it, in the synthesis of "commercially valuable products".