http://www.netl.doe.gov/publications/factsheets/project/FE0004498.pdf
First, we remind you of a very recent dispatch, now accessible on the West Virginia Coal Association's web site via the link:
which concerned:
"US Patent Application 20130048506 - Electrodes for High Efficiency Aqueous Reduction of CO2; 2013; Assignee: The Trustees of Columbia University in the City of New York; Abstract: An electrolytic cell system to convert carbon dioxide to a hydrocarbon ... wherein the hydrocarbon (produced) is ethylene". Sadly, as we have several times pointed out, official US Government links to official US Government electronic files of US Patent Applications very often prove unreliable, and wind up connecting, once those links are published, with totally unrelated documents. That has proven true in the above-cited report; and, although links to secondary site records of "US Patent Application 20130048506 - Electrodes for High Efficiency Aqueous Reduction of CO2" which are included in that report still function properly, we are attaching to this dispatch our own electronic file of the document, so that it will remain accessible, if needed by anyone, via the Coal Association.
Perhaps even more sadly, we note in passing, the same is proving true now even of the US Government's links to issued patents; and, we will make note of those problems as we discover them and as they relate to future reports.
In any case, as we indicated in our report of "US Patent Application 20130048506 - Electrodes for High Efficiency Aqueous Reduction of CO2", the synthesis of Ethylene from Carbon Dioxide, or, as seen in:
West Virginia Coal Association | DuPont 1952 Ethylene from Coal | Research & Development; concerning:
"United States Patent 2,623,011 - Preparation of Olefins by Coal Carbonization; 1952; Assignee: E.I. DuPont and Company; Abstract: This invention relates to an improved process for the preparation of unsaturated hydrocarbons, and more particularly, to the preparation of ethylene by the carbonization of coal";
from Coal, can enable the productive recycling and chemical transformation of even more Carbon Dioxide.
Ethylene made, via the process of "US Patent Application 20130048506", from Carbon Dioxide, or, via the process of "United States Patent 2,623,011", from Coal, can be reacted with even more Carbon Dioxide, with both the Ethylene and the additional Carbon Dioxide being transformed into very valuable plastics.
And such processes, we advise, would be different from and in addition to other CO2-to-Plastics processes about which we've reported, such as, for one example, seen in:
West Virginia Coal Association | Bayer Is Converting Coal Power Plant CO2 Into Plastics | Research & Development; concerning, in part, the article: "'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".
As an additional note in passing, if you have followed our reports at all, you might know that the above Bayer Corporation is pretty-danged serious about establishing the fact of the matter, which is: Carbon Dioxide, as it arises in only a very small way, relative to natural sources of emission, such as the Earth's inexorable processes of planetary volcanism, from our essential use of Coal in the generation of truly abundant and genuinely affordable electric power, is a valuable raw material resource.
In reports to follow, we'll see how Bayer, may the Good Lord bless 'em, is beginning to hammer that point home to sort of the "nth" degree.
Herein, though, we learn that the United States Department of Energy, through their National Energy Technology Laboratory, or Laboratories, has begun to further examine and develop, through contracted research conducted by some well-known universities commonly thought of as members of the elite "Ivy League", the technology for combining Ethylene, as can be made from Carbon Dioxide, with even more Carbon Dioxide, in order to synthesize another class of plastics known broadly as "Acrylates".
As seen in excerpts, with additional links and excerpts appended, from the initial link in this dispatch to:
"'Chemical Fixation of CO2 to Acrylates Using Low-Valent Molybdenum Sources'
Background: In an effort to reduce carbon dioxide (CO2) emissions from various industrial and power generation processes to the atmosphere, the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL) is currently funding research intended to advance current state-of-the-art technologies that address the use of CO2 in a variety of different economic and industrial processes.
Carbon dioxide utilization efforts focus on pathways and novel approaches for reducing CO2 emissions by developing beneficial uses for CO2 that will mitigate emissions in areas where geologic storage may not be the optimal solution.
(Pretty tough for us to see how "geologic storage" could ever, in any "areas" or in any way shape or form, be an "optimal solution". Our guess is that a lot of time and ink has been wasted on it at the behest of Big Oil, who wants to saddle the costs of secondary petroleum extraction, through the injection of CO2 into nearly-depleted natural petroleum reservoirs, onto the backs of consumers of Coal-based electrical power; and, so much time and ink was wasted on promoting the concept that perfunctory genuflections to it still have to be made, like bowing or curtseying to now-powerless, figurehead royalty when you're introduced to them.)
Utilization is an important component in carbon sequestration and some of the applicable approaches are conversion of CO2 into useful chemicals and polycarbonate plastics; storage of CO2 in solid materials having economic value; indirect storage of CO2, and other breakthrough concepts.Critical challenges identified in the utilization focus area include the cost- effective use of CO2 as a feedstock for chemical synthesis or its integration into pre-existing products. The efficiency (CO2 integration reaction rate and the amount of CO2 sequestered in a product) and energy use (the amount of energy required to utilize CO2 in existing products) of these utilization processes also represent a critical challenge.
This project will provide core research and development necessary for producing low-valent molybdenum catalysts to establish CO2 as a reactant in the production of acrylate (an organic chemical) compounds.
Project Description: Researchers at Brown University are assessing the viability of CO2 reduction with ethylene using low-valent molybdenum as a catalyst to produce acrylic acid or valuable acrylate compounds.
(As per our introductory comments, note the use of "ethylene", which can itself, as in our report of "US Patent Application 20130048506 - Electrodes for High Efficiency Aqueous Reduction of CO2", be made from Carbon Dioxide.)
The potential environmental and economic advantages of producing acrylates from CO2 and ethylene have spurred substantial research into catalysts to promote this transformation. Over the past twenty-plus
years, a select number of transition metal complexes have shown the ability to couple CO2 and ethylene, with molybdenum complexes demonstrating particular promise by forming acrylate hydride complexes.
Project Facts: Wesley Bernskoetter, Principal Investigator; Brown University, Providence, Rhode Island
Start Date: 10/1/2010; End Date: 9/30/2012
(We'll double-check, and keep checking, but the final report doesn't yet seem to be available. We will get it to you when it is published by the DOE.)
A catalytic cycle is a series of chemical reactions involving a catalyst that, at the end of the cycle, is returned to its initial state rather than being consumed in the reaction process; with cycle closure, the catalyst may be reused repeatedly.
Researchers believe that such a cycle is achievable for CO2/ethylene coupling, in the case of these acrylate hydride complexes, lacking only reductive formation of an oxygen-hydrogen (O-H) bond for closure. The outcome of the catalyzed process, besides catalyst restoration, should be the desired product. Disappointingly, elimination of free acrylic acid has yet to be observed for any complex capable of uniting CO2 and ethylene.
Given the time span of research in this field, the absence of acrylic acid extrusion raises legitimate questions about the validity of this approach, despite computational evidence suggesting that the process has a slight thermodynamic favorability. This project outlines a systematic evaluation of those factors and mechanisms which may impact the kinetics of reductive O-H elimination from acrylate hydride complexes en route to providing definitive assessment of the potential for acrylic acid production in this manner.
The goal of the work is to provide core research and development necessary for establishing whether low-
valent molybdenum catalysts will enable viability of CO2 as a reactant in the production of acrylate compounds. This project will be an interdisciplinary laboratory study with three phases:
1. Scope of CO2 and ethylene coupling: This research will expand the range of molybdenum complexes
capable of coupling CO2 and ethylene by defining the available ligand (a molecule bonded to a central metal
atom) architectures which facilitate acrylate formation. The approach for this effort will synthesize two sets
of molybdenum complexes shown by computational analysis to provide promising reaction thermodynamics
and compare the relative reactions in CO2 and ethylene coupling of each using multiple spectroscopic methods.
2. Reductive Elimination of Acrylate Products: This phase will evaluate computational and experimental
investigations to determine the catalytic parameters necessary to enhance reductive acrylate elimination.
This approach will utilize molybdenum complexes developed in Phase I via comparative rate experiments
and mechanistic probes to access the relative importance of multiple variables which determine the favorability of reductive acrylate elimination.
3. Design and prepare an optimized molybdenum catalyst for a bench-scale reaction to test the feasibility of
molybdenum catalyzed acrylate formation from CO2: This approach will correlate the structure and reactivity
relationships in ligand supports for molybdenum found to be most influential in Phases I and II. In addition, the research will determine the ligand architecture that best fits those correlations, and then synthesize complex(es) which provide the optimal opportunity for efficient catalytic acrylate formation.
Benefits: This research will identify the critical factors in CO2/ethylene coupling and catalyst design, specifically evaluating ligand attributes and reaction conditions which are critical to enabling acrylate elimination from the metal center. This project will yield the understanding needed to optimize supporting platforms for molybdenum catalysts and should enable assessment of the viability of this production method.
If the process is established, it will enable the utilization of significant quantities of CO2 in acrylate production, economically reducing atmospheric levels of this important greenhouse gas."
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In case you aren't familiar with "acrylate", or acrylic plastics in general, background is accessible via:
Acrylate - Wikipedia, the free encyclopedia; Acrylic resin - Wikipedia, the free encyclopedia; and:
Acrylate polymer - Wikipedia, the free encyclopedia: "Acrylates are the salts and esters of acrylic acid. They are also known as propenoates (since acrylic acid is also known as 2-propenoic acid). Acrylates contain vinyl groups, that is, two carbon atoms double bonded to each other, directly attached to the carbonyl carbon. Acrylates and methacrylates (the salts and esters of methacrylic acid are common monomers in polymer plastics, forming the acrylate polymers".
We confess that we were unable to find reliable statistics concerning how much of it is used, or, what the true size of the potential market for such Acrylic, and Acrylic compounds, could be, a subject of special interest if Acrylates were to wind up being made from, essentially, Carbon Dioxide, via the initial synthesis of Ethylene from CO2 and the subsequent reaction of Ethylene with more CO2. However, the information available via the Wikipedia articles concerning the current applications and uses for Acrylates and Acrylate Polymers should, in general, give you some idea that this could be a truly significant consumer of reclaimed and recycled Carbon Dioxide.
As we noted, final technical reports still seem to be pending; and, we'll get them to you as soon as they become available, or when we're able to overcome our personal insufficiencies and track them down.
However, preliminary indications that have begun to publicly appear are, that, Brown University, and their less-publicized partner, Yale University, another charter member of the Ivy League - Wikipedia, the free encyclopedia, have, indeed, established the "viability of CO2 as a reactant in the production of acrylate compounds".
As seen in:
CO2 may be cheaper source of valuable chemicals | Brown University News and Events
""'CO2 Could Produce Valuable Chemical Cheaply'
March 21, 2013
A possible use for excess carbon: In the presence of nickel and other metal catalysts, CO2 and ethylene gas form an acrylate precursor configured in a five-membered ring. The challenge has been to crack that ring open, allowing a carbon-carbon double bond to form, creating acrylate. Lewis acids do the trick.
(We've previously reported on the utility of "Lewis" acids and bases in some Carbon conversion technologies. We can't explain the nature of their chemical nature and reactivity, but, they are well-known and have been utilized in various chemical processes for nearly a century, since the 1920's. More can be learned via:
The Lewis Definitions of Acids and Bases; and: Lewis acids and bases - Wikipedia, the free encyclopedia.)
Researchers at Brown and Yale have demonstrated a new “enabling technology” that could use excess carbon dioxide to produce acrylate, a valuable commodity chemical involved in the manufacture of everything from polyester cloth to disposable diapers.
Brown University: A key advance, newly reported by chemists from Brown and Yale Universities, could lead to a cheaper and more sustainable way to make acrylate, an important commodity chemical used to make materials from polyester fabrics to diapers.
Chemical companies churn out billions of tons of acrylate each year, usually by heating propylene, a compound derived from crude oil. “What we’re interested in is enhancing both the economics and the sustainability of how acrylate is made,” said Wesley Bernskoetter, assistant professor of chemistry at Brown, who led the research. “Right now, everything that goes into making it is from relatively expensive, nonrenewable carbon sources.”
(The above statement that "companies churn out billions of tons of acrylate each year" might be a tad bit of an inadvertent exaggeration. Millions of tons, yes.)
Since the 1980s researchers have been looking into the possibility of making acrylate by combining carbon dioxide with a gas called ethylene in the presence of nickel and other metal catalysts. CO2 is essentially free and something the planet currently has in overabundance. Ethylene is cheaper than propylene and can be made from plant biomass.
There has been a persistent obstacle to the approach, however. Instead of forming the acrylate molecule, CO2 and ethylene tend to form a precursor molecule with a five-membered ring made of oxygen, nickel, and three carbon atoms. In order to finish the conversion to acrylate, that ring needs to be cracked open to allow the formation of a carbon-carbon double bond, a process called elimination.
Wesley Bernskoetter: "We thought that if we could find a way to cut the ring chemically, then we would be able to eliminate (nickel and oxygen) very quickly and form acrylate, and that turns out to be true."
That step had proved elusive. But the research by Bernskoetter and his colleagues, published in the journal Organometallics, shows that a class of chemicals called Lewis acids can easily break open that five-membered ring, allowing the molecule to eliminate and form acrylate.Lewis acids are basically electron acceptors. In this case, the acid steals away electrons that make up the bond between nickel and oxygen in the ring. That weakens the bond and opens the ring.
"We thought that if we could find a way to cut the ring chemically, then we would be able to eliminate very quickly and form acrylate," Bernskoetter said. "And that turns out to be true."
He calls the finding an "enabling technology" that could eventually be incorporated in a full catalytic process for making acrylate on a mass scale. "We can now basically do all the steps required," he said.
From here, the team needs to tweak the strength of the Lewis acid used. To prove the concept, they used the strongest acid that was easily available, one derived from boron. But that acid is too strong to use in a repeatable catalytic process because it bonds too strongly to the acrylate product to allow additional reactions with the nickel catalyst.
"In developing and testing the idea, we hit it with the biggest hammer we could,” Bernskoetter said. “So what we have to do now is dial back and find one that makes it more practical."
There’s quite a spectrum of Lewis acid strengths, so Bernskoetter is confident that there’s one that will work. "We think it’s possible," he said. "Organic chemists do this kind of reaction with Lewis acids all the time."
The ongoing research is part of a collaboration between Brown and Yale supported by the National Science Foundation’s Centers for Chemical Innovation program. The work is aimed at activating CO2 for use in making all kinds of commodity chemicals, and acrylate is a good place to start.
"It’s around a $2 billion-a-year industry,” Bernskoetter said. “If we can find a way to make acrylate more cheaply, we think the industry will be interested."
Other authors on the paper were Dong Jin and Paul Willard of Brown and Nilay Hazari and Timothy Schmeier of Yale.""
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Concerning the lead researcher, Brown's Wesley Bernskoetter, who earned his doctorate at Cornell University, have a look at his research interests, via:
Faculty Profile: Wesley Bernskoetter, PhD, Cornell University | Alpert Medical School; "Research in the Bernskoetter lab focuses on the use of inorganic and organometallic complexes to address challenges relevant to our planet's growing energy concerns. Our initiatives employ techniques from synthetic organic and inorganic chemistry to study highly reactive molecules capable of mediating difficult chemical transformations"; and:
The Directory of Research and Researchers at Brown: Wesley Bernskoetter; wherein some of his specific projects are detailed to include:
"Department of Energy, National Energy Technology Laboratory, Chemical Fixation of CO2 to Acrylates Using Low Valent Molybdenum Sources, Principal Investigator.
Department of Defense, Air Force Office of Scientific Research, Acrylate Formation from CO2 and Ethylene by Tandem Molybdenum and Palladium Catalysis, Principal Investigator.
National Science Foundation, Centers for Chemical Innovation, CO2 as a Sustainable Feedstock for Chemical Commodities. Co-Principal Investigator."
To be clear:
Carbon Dioxide can be converted into Ethylene; and, that Ethylene can then be reacted with more Carbon Dioxide to synthesize Acrylics, or "Acrylates", a family of plastics and plastic resins with broad utility and many applications, wherein any Carbon Dioxide consumed in the Acrylate synthesis, both through the initial synthesis of Ethylene and the subsequent reaction of that Ethylene with more Carbon Dioxide, would be forever, permanently and profitably, "sequestered".
Carbon Dioxide is a valuable, maybe even a precious, raw material resource.