United States Patent: 8093351

We herein reintroduce a technical concept and process for the utilization and consumption of Carbon Dioxide, one which results in the synthesis of a high-value product wherein the CO2 is permanently, and very productively, "sequestered".

And, we regret, that, since we have more lately been focusing, in our reports concerning the productive utilization of Carbon Dioxide, on those technologies, as seen for example in our reports of:

West Virginia Coal Association | USDOE Sunlight Converts CO2 into Methane | Research & Development; concerning: "US Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation; 2013; Inventor: Brian Ingram, et. al., IL and TN; Assignee: UChicago Argonne, LLC, Chicago; Abstract: In one preferred embodiment, a photocatalyst for conversion of carbon dioxide and water to a hydrocarbon and oxygen ... . Government Interests: The United States Government has rights in this invention pursuant to Contract No. DE-AC02-06CH11357 between the United States Government and UChicago Argonne, LLC representing Argonne National Laboratory. This invention relates to the energy efficient photocatalytic conversion of carbon dioxide gas and water vapor to methane and other hydrocarbon fuels, particularly promoted by sunlight"; and:


West Virginia Coal Association | USDOE Converts Atmospheric CO2 into Gasoline | Research & Development; concerning: "United States Patent Application 20100205856 - Method of Producing Synthetic Fuels and Organic Chemicals from Atmospheric Carbon Dioxide; 2010; Assignee: Los Alamos National Security LLC, NM; Abstract: The present invention is directed to providing a method of producing synthetic fuels and organic chemicals from atmospheric carbon dioxide. Carbon dioxide gas is extracted from the atmosphere, hydrogen gas is obtained by splitting water, a mixture of the carbon dioxide gas and the hydrogen gas (synthesis gas) is generated, and the synthesis gas is converted into synthetic fuels and/or organic products. Government Interests: This invention was made with government support under Contract No. DE-AC52-06NA25396 awarded by the U.S. Department of Energy. The government has certain rights in the invention. Claims: A method for producing a chemical product comprising the steps of: extracting carbon dioxide gas from the atmosphere; producing hydrogen gas; combining said carbon dioxide gas and said hydrogen gas to produce a synthesis gas; and converting said synthesis gas to said product. The method ... wherein said method is powered by a power source selected from the group consisting of ... hydroelectric power, geothermal power, wind power, photovoltaic solar power, thermal solar power, and combinations thereof (and) wherein said product is ... diesel fuel, jet fuel, gasoline, petrochemicals, plastics, butane, methanol, ethylene, propylene, aromatic compounds, petrochemical derivatives, derivatives thereof, and mixtures thereof";

that utilize one form of environmental energy or another to convert Carbon Dioxide into a substitute for natural gas Methane, which many astute scientists report isn't nearly as economically abundant in deep shale deposits as some would have us for whatever reason believe, and, into various other hydrocarbons, some of them liquid hydrocarbons including, even, Gasoline and Diesel fuel; we haven't done as good a job as we should demonstrating and documenting as well the fact that Carbon Dioxide can also be productively utilized and chemically, permanently, consumed in the synthesis of certain high-value plastics.

But, absent now the help of some of technically-astute folks who used to guide and advise us in these efforts, and given our own sadly limited capacities, we'll have to be very conservative in the way we address the topic, resorting in large part to generalizations.

And, here, to kick things off, is one of those generalizations:

Carbon Dioxide, as is emitted in only small way, relative to some natural sources of emission - - such as the Earth's inexorable processes of planetary volcanism, the vast bulk of which take place unseen and unaccounted for deep, deep beneath the surface of the oceans - - from our essential use of Coal in the generation of abundant and genuinely affordable electric power, is a valuable raw material resource.

We can recover Carbon Dioxide from whatever source convenient to us, and then use and consume that Carbon Dioxide in the synthesis of valuable, high-performance polymers; that is, "plastics"; plastics that are used in high volumes in all sorts of industrial and consumer applications.

And, note, as we proceed in this and future discussions of such CO2 utilization technology, we will be bandying about terms like "plastics" and "polymers", or "resins", almost interchangeably, and, in some, perhaps many, cases, somewhat inaccurately.

Our wan hope is that some member of the Coal Country press corps will finally be motivated enough to disengage his or her nose from the gas pipe, and seek out one of our many genuine experts in academia or industry to explain it all to them; and, then, report it fully and accurately to the rest of us.

Then, we might have enough information, enough facts, available to us for us to properly instruct our elected, office-holding employees as to what topics we most want addressed, and how we want those topics to be addressed, in the halls of our government.

With that thought in mind, we interject here what will perhaps for many, at least we know for some, be  unwelcome commentary.

For those of you who might have followed our reports over these past years, as they appear on the West Virginia Coal Association's web site, and, as they remain available in the Coal Association's R&D archives, you might be surprised to learn that each and every one of those reports has been addressed and sent primarily to a collection of half a dozen or so Coal Country commercial journalists; none of whom, apparently, believes that the facts:

that, Coal can be, and is in other parts of the world being, converted into any and all forms of the liquid hydrocarbon fuels we in the US remain enslaved to OPEC for our supply of;

that, Carbon Dioxide can be reclaimed from industrial exhaust or from the atmosphere itself and then, too, be, as it is in other parts of the world being, converted into any all forms of gaseous and liquid hydrocarbons;

and: that, Coal Ash can be mined for important metals like Aluminum and/or be used and consumed in the making of high performance cement and concrete;

are of much, if any, importance to the citizens of United States Coal Country, much less to the United States of America as a whole.

To those journalists, and to you, as well, we call upon one of America's great orators, a hero to many and, regardless of what any one of you might think of him personally, a man of intellect and courage, to speak plainly and bluntly to the overriding moral truth governing the issue of keeping, for whatever reason, silent about the Truth, especially when that Truth could be of so much benefit to so many, and, when continuing to keep silent about that Truth aids, abets, and defends ongoing harm:

In a speech entitled "Beyond Vietnam: A Time To Break Silence", delivered in New York City on April 4, 1967:

A Time to Break Silence: By Rev. Martin Luther King;

the Reverend Martin Luther King said, among other things:

"A time comes when silence is betrayal".

From our perspective here, for a number of reasons, that 'time" came and went some years ago. But, there is still "Time to Break Silence", and to redress omissions; although, time, for all of us, eventually runs out.

That said, presuming some of you to have followed our posts thus far, you will know that some dynamic and leading corporations are starting to treat Carbon Dioxide as an industrial raw material resource for the manufacture of plastics and polymers; as seen, for one example, in our report of:

West Virginia Coal Association | Bayer Is Converting Coal Power Plant CO2 Into Plastics | Research & Development; concerning: "'Bayer Material Science CO2-to-Plastics Pilot Plant'; 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. The process technology was developed on a laboratory-scale for the first time to produce polymer materials from CO2. Bayer aims to use CO2 as an alternative to production of polymer materials from fossil fuels".

And, in addition to companies like Bayer Corporation, some leading institutions of higher learning are, as well, promulgating that fact that Carbon Dioxide, even as extracted "from the waste gas released during power generation", can be profitably utilized as a raw material for the synthesis of plastics, as seen in:

West Virginia Coal Association | CO2 to Plastics | Research & Development; "A Cornell University research group has made a sweet and environmentally beneficial discovery - - how to make plastics from citrus fruits, such as oranges, and carbon dioxide. ... Geoffrey Coates, a Cornell professor of chemistry and chemical biology, and his graduate students Chris Byrne and Scott Allen describe a way to make polymers using limonene oxide and carbon dioxide ... . By using their catalyst to combine the limonene oxide and CO2, the Coates group produced a novel polymer - called polylimonene carbonate - that has many of the characteristics of polystyrene, a petroleum-based plastic currently used to make many disposable plastic products"; and:

West Virginia Coal Association | USDOE Announces Plastics Made from Carbon Dioxide | Research & Development; "'Recycling Carbon Dioxide to Make Plastics'; May 20, 2013; Novomer’s thermoplastic pellets incorporate waste CO2 into a variety of consumer products. ... The Cornell University spinoff’s technology centers on a catalyst that converts carbon dioxide into a polymer that could be used to make everyday items such as packaging, cups, and forks. The plastic, which was originally created by Cornell chemist Geoffrey Coates, is also safe and strong enough to be used in medical implants and devices.The plastic should be relatively inexpensive since carbon dioxide is a cheap feedstock, says Coates"; . The plastic is being made on a pilot scale, and Novomer declines to give details of its commercial-scale manufacturing plans. Novomer president Charles Hamilton says that, while it is hard to predict the product’s final cost, it should be cost competitive with traditional petroleum-based plastics".

Further, as revealed in the above reports, the Cornell University development of such Carbon Dioxide utilization technologies, which led to the formation of the company "Novomer" to commercialize them, was funded by the United States Government.

Novomer, as it happens, has continued to develop the Cornell University Carbon Dioxide recycling technologies, in partnership with Cornell professor Geoffrey Coates; and, we will address Novomer's further activities in reports to follow. But, herein, we document one of Coates' and Cornell's key processes for the conversion of Carbon Dioxide into versatile polymers that, in terms of cost and performance, are "competitive with traditional petroleum-based plastics".

As seen in excerpts from the initial link in this dispatch to.

"United States Patent 8,093,351 - Copolymerization of Propylene Oxide and Carbon Dioxide

Patent US8093351 - Copolymerization of propylene oxide and carbon dioxide and ... - Google Patents

Copolymerization of propylene oxide and carbon dioxide and homopolymerization of propylene oxide - Cornell Research Foundation

Date: January 10, 2012

Inventors: Geoffrey Coates, et. al., NY

(Note that the lead named inventor, Cornell University Professor Geoffrey Coates, has been at work on the development of Carbon Dioxide utilization technologies for some time. And, his CO2-utilization efforts have been recognized and acknowledged by other branches of the United States Government, as well; including the United States Environmental Protection Agency; as seen in:

2012 Academic Award (Coates) | Green Chemistry | US EPA; "Green Chemistry; US EPA 2012 Academic Award; Professor Geoffrey Coates of Cornell University; 'Synthesizing Biodegradable Polymers from Carbon Dioxide and Carbon Monoxide'; Carbon monoxide and carbon dioxide derived from biomass or other carbon sources are ideal feedstocks for chemicals, but there had been no efficient way to make them into valuable polymers. Professor Coates developed a family of catalysts that convert carbon dioxide and carbon monoxide into polymers. Novomer, Inc. is using his discoveries to develop a range of innovative, high-performance products, including can and coil coatings, adhesives, foams, and plastics".

We'll be discussing the "and Carbon Monoxide" side of things in more detail in coming reports concerning "Novomer, Inc." itself, since, as seen for only one example in:

West Virginia Coal Association | Bayer Improves Coal + CO2 = Carbon Monoxide | Research & Development; concerning: "United States Patent 7,473,286 - Carbon Monoxide Generator; 2009; Assignee: Bayer Material Science, AG, Germany; The present invention relates to a novel generator for the reaction of carbon-containing raw materials and also to an improved process for the production of carbon monoxide gas (CO gas) having a high degree of purity using such a generator. Carbon monoxide gas is frequently produced in the art by means of a continuous process in which carbon-containing raw materials are reacted with oxygen and carbon dioxide ... . An object of the present invention was ,,, to provide a continuous process for the production of CO gas by the gasification of coal";

the technology exists to readily manufacture Carbon Monoxide from Carbon Dioxide.)

Assignee: Cornell (University) Research Foundation, Ithaca, NY

Abstract: Copolymers of propylene oxide and carbon dioxide and homopolymers of propylene oxide are made using two dimensional double metal cyanide complexes having the formula Co[M(CN)4 or hydrated or partially dehydrated form thereof. There is no propylene carbonate by-product in the copolymerization.

Government Interests: This invention was made at least in part with U.S. Government support under NSF grant numbers CHE-0243605 and DMR-0079992. The Government has certain rights in the invention.

Claims: A method comprising the step of polymerizing ... propylene oxide and optionally carbon dioxide in the presence of a catalytically effective amount of Cobalt[M(Cyanide)4, wherein M is selected from the group consisting of Nickel, Palladium, Platinum and combinations thereof ... . 

The method ... wherein the copolymerization is carried out at a carbon dioxide pressure ranging from ambient pressure to 1500 psig. 

The method ... wherein the temperature of reaction ranges from 10 C to 150 C. 

The method ... of copolymerizing propylene oxide and carbon dioxide.

Background and Field: This invention is directed to homopolymerization of propylene oxide and copolymerization of propylene oxide and carbon dioxide, using double metal cyanide catalysts. 

Zinc hexacyanometalates have been used for epoxide/carbon dioxide copolymerization. A drawback to these catalysts is that undesired by-product propylene carbonate (requiring purification) is also formed unless such low temperatures are utilized that catalyst activity is significantly reduced.

(Note that the needed "propylene oxide" is, generically, an "epoxide"; and, there are many natural epoxides, such as the "limonene" noted in our introductory references to our prior reports concerning the development of CO2-recycling and use technologies at Cornell University. Natural, botanical epoxides, like "limonene", would of course represent an additional, albeit indirect, recycling of CO2 via the photosynthetic processes that naturally produced the limonene, or it's relatives. As we will document in reports to follow, there are additional routes for the synthetic manufacture of the needed epoxides, like the specified "propylene oxide", which synthesis routes themselves can be structured and designed to consume even more CO2.) 

Summary: It has been discovered herein that (specified) metal cyanide complexes readily catalyzed the copolymerization of propylene oxide and carbon dioxide without the formation of propylene carbonate. These complexes are also functional to catalyze the homopolymerization of propylene oxide. 

In one embodiment of the invention herein ... the invention is directed to a method for the non-alternating copolymerization of propylene oxide and carbon dioxide to produce ... poly(propylene oxide)."

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It is difficult to overemphasize the importance of the end product made herein, via the Cornell University process of "United States Patent 8,093,351", from Carbon Dioxide. Some inkling can be gained from:

Polypropylene glycol - Wikipedia, the free encyclopedia; "Polypropylene glycol or polypropylene oxide is the polymer of propylene glycol";

wherein some global production numbers are presented. In essence, as we will document in reports to follow, the "polypropylene oxide", although itself a "polymer" in the strictest sense, is intended for further reaction with other plastics precursors, some of which can themselves be manufactured using CO2 as a basic raw material, for final conversion into completed polymers, or plastics, such as polyurethane, in which any Carbon Dioxide that had been consumed as a raw material would remain chemically and permanently, productively and profitably, "sequestered".

Again, there are multiple routes inherent in the entire process, and in follow-on processes, for the, potential, recycling, or just use and consumption, of Carbon Dioxide. And, it seems to us, here, that complete manufacturing industries could be established based on that use and consumption of Carbon Dioxide.

We'll do our inadequate best to define and describe those potentials in reports to follow, but, for now, let it stand, as confirmed again herein by Cornell University, in their disclosure of "United States Patent 8,093,351", that: Carbon Dioxide, as it arises in only a small way, relative to some natural sources of emission, such as the Earth's inexorable, and un-taxable, processes of planetary volcanism, from our essential use of Coal in the generation of abundant and truly affordable electric power, is a valuable raw material resource. We can reclaim it from whatever convenient source, and, then, as herein, convert it directly into polymeric materials used worldwide in the manufacture of commodity plastics.


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