North Dakota Converts CO2 into High-Performance Polymer

United States Patent Application: 0140024800

We've documented for you previously, as in, for just several examples, our reports of:

Bayer Is Converting Coal Power Plant CO2 Into Plastics | Research & Development | News; concerning a report about the German parent of our Pittsburgh, PA, Bayer Corporation: "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. The Leverkusen pilot plant will test a new   process technology on technical scale for producing raw material of polyurethane. ... 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. 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. The CO2 feedstock   for the pilot plant will be supplied from a lignite power plant in   Niederaussem, operated by RWE Power. The Niederaussem Coal Innovation Center   at the plant, also operated by the utility company, has a CO2 scrubbing system for separating it from flue gases"; and:

 

Cornell University Uses CO2 to Synthesize Plastics | Research & Development | News; concerning: "United States Patent 8,093,351 - Copolymerization of Propylene Oxide and Carbon Dioxide; Date: January 10, 2012; Inventors: Geoffrey Coates, et. al., NY; Assignee: Cornell (University) Research Foundation; 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.  The method ... of copolymerizing propylene oxide and carbon dioxide. ... This invention is directed to homopolymerization of propylene oxide and copolymerization of propylene oxide and carbon dioxide, using double metal cyanide catalysts. 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)"; and, concerning the Cornell University commercial spin-off:

USDOE Announces Plastics Made from Carbon Dioxide | Research & Development | News; concerning: "Recycling Carbon Dioxide to Make Plastics; May 20, 2013; Novomer’s thermoplastic pellets incorporate waste CO2 into a variety of consumer products. By using CO2 that would otherwise be emitted to the atmosphere, the process has the potential to cut greenhouse gas emissions while simultaneously reducing petroleum consumption and producing useful products for American consumers. The world’s first successful large-scale production of a polypropylene carbonate (PPC) polymer using waste carbon dioxide (CO2) as a key raw material has resulted from a projected funded in part by the U.S. Department of Energy's Office of Fossil Energy. The PPC polymer production run, conducted by Novomer in collaboration with specialty chemical manufacturer Albemarle Corporation (Orangeburg, SC), tested scale-up of Novomer’s novel catalyst technology. Requiring only minor modifications to existing Albemarle facilities, the run produced seven tons of finished polymer, which will be used to accelerate product qualification. The Novomer process uses a catalyst to create PPC polymers through the co-polymerization of CO2 and chemicals called epoxides. The process results in polymers containing more than 40 percent CO2 by weight. The CO2-containing polymers can be tailored for applications with a broad range of material characteristics from solid plastics to soft, flexible foams, depending on the size of the polymer chain. Novomer is positioning its new polymer technology to compete with conventional petroleum-based raw materials across a diverse range of applications, including flexible, rigid, and microcellular packaging foams, thermoplastics, polyurethane adhesives and sealants, and coating resins for food and beverage cans";

that, Carbon Dioxide, as it arises in only a small way, relative to some all-natural and un-taxable sources of it's emission, such as the Earth's inexorable processes of planetary volcanism, from our essential use of Coal in the generation of truly abundant and truly affordable electric power, is a valuable raw material resource.

We can - - as the admirable Bayer Corporation is demonstrating on a practical basis, as in our above-cited report concerning the "Bayer Material Science CO2-to-Plastics Pilot Plant, Germany" - - recover Carbon Dioxide and then use that CO2 "as a substitute for ... petroleum" raw materials in the "production of plastics".

We'll note that the processes for such use of Carbon Dioxide, as embodied variously by the Bayer and the Cornell, and the Novomer technologies, resulting in the synthesis of both "polyurethane" and "polypropylene carbonate" materials, are different in significant respects, although there are materials known as polypropylene carbonate "polyols" that are themselves useful in the compounding of polyurethanes. 

And, as seen in our report of: 

Bayer Improves Coal + CO2 = Carbon Monoxide | Research & Development | News; concerning: "United States Patent 7,473,286 - Carbon Monoxide Generator;  2009; Assignee: Bayer Material Science, AG, Germany";

Bayer has developed technology for making Carbon Monoxide out of Carbon Dioxide and Coal, with Carbon Monoxide also being a valuable raw material in the synthesis of even additional polymers and plastics, or the raw materials from which polymers, including polyurethane, can be compounded.

The chemistries are immensely complex, at least for our sadly limited capacities, and, absent now the kind services of some of the knowledgeable folk who used to advise us, any further explanation we might attempt to make would be woefully inadequate, and perhaps misleading.

However, herein we see that the University of North Dakota has, as well, under contract, like Cornell University in our above-cited reports, to an agency of the United States Government, been developing similar and related technologies for the productive consumption and use of Carbon Dioxide in the synthesis of high-performance polymers; that is, plastics, wherein the Carbon Dioxide consumed would remain forever, and profitably and productively, "sequestered".

Comment follows and is inserted within excerpts from the initial link in this dispatch to the recent:

"US Patent Application 20140024800 - CO2  Capture and Conversion to a Carbamate Salt and Polyurea

CARBON DIOXIDE CAPTURE AND CONVERSION TO A CARBAMATE SALT AND POLYUREA - UNIVERSITY OF NORTH DAKOTA

Patent US20140024800 - Carbon dioxide capture and conversion to a carbamate salt and polyurea - Google Patents

Date: January 23, 2014

Inventor: Qianli Chu, North Dakota

Assignee: The University of North Dakota, Grand Forks

(Note that we have cited the University of North Dakota and their development of Coal conversion and Coal  utilization technologies many times, as, for one example, in our report of:  

North Dakota Converts Coal and Biomass to Gasoline for USDOE | Research & Development | News; concerning: "United States Patent Application 20130338411 - Liquefaction of Carbonaceous Material and Biomass to Produce a Synthetic Fuel; December 19, 2013; Inventor: Ramesh K. Sharma, ND; Abstract: The present invention relates to production of fuels from carbonaceous material and biomass. In some examples, the carbonaceous material is nonpetroleum fossil fuel or petroleum residuals. Various embodiments of the present invention provide a method of liquefaction of carbonaceous material and biomass. The method includes providing or obtaining a feed mixture, the mixture including carbonaceous material and biomass. The method also includes subjecting the feed mixture to liquefaction, to provide a product slurry. Various embodiments of the present invention provide a method of fuel production from carbonaceous material and biomass. The method includes separating the product slurry from the liquefaction, to give a conversion component. The method also includes processing the conversion component, to give a fuel.  Government Interests: This invention was made with government (by the) U.S. Department of Energy (DOE) Cooperative Agreement No. DE-FC26-0SNT43291 .... . The government has certain rights in this invention. Claims; A method of liquefaction of carbonaceous material and biomass, comprising: providing or obtaining a feed mixture, the mixture comprising carbonaceous material and biomass; and subjecting the feed mixture to liquefaction, to provide a product slurry; wherein the carbonaceous material comprises a nonpetroleum fossil fuel (and) wherein the carbonaceous material comprises coal, coal tar ... or a combination thereof. The method ... wherein the coal comprises coal powder, pulverized coal, or a combination thereof (and) wherein the coal comprises lignite, brown coal, jet coal, subbituminous coal, bituminous coal, steel coal, anthracite, graphite, or a combination thereof (and) wherein the biomass comprises plant-derived oil, algae-derived oil, biomass pyrolysis oil, waste oil, yellow grease, brown grease, tar, or animal fat (and) wherein the mass ratio of carbonaceous material to biomass is about 0.01-10 to 1. ... A method of fuel production from carbonaceous material and biomass ... wherein the fuel comprises a liquid transportation fuel. A method of liquefaction of coal and biomass, comprising: providing or obtaining a feed mixture, the mixture comprising coal and biomass, the biomass comprising plant-derived oil, algae-derived oil, biomass pyrolysis oil, waste oil, yellow grease, brown grease, tar, or animal fat; and subjecting the feed mixture to liquefaction (as described). Various embodiments of the present invention provide a method of producing a synthetic fuel ... from ... coal, and renewable material (and, by) controlling the composition of the product fuel, various fuels can be produced, such as, for example, gasoline, naptha, kerosene, jet fuel, or diesel fuel".)

Abstract: A method for treating carbon dioxide includes preparing a polyamine composition and delivering a stream containing carbon dioxide to the polyamine composition. The carbon dioxide reacts with polyamine in the polyamine composition to form a carbamate salt. A method for producing polyurea from carbon dioxide includes delivering a stream containing carbon dioxide to a polyamine composition. The carbon dioxide reacts with polyamine in the polyamine composition to form a carbamate salt. The method also includes dehydrating the carbamate salt to produce polyurea.

(If you're not familiar with the term "polyurea", it is, or can be, a very high-performance polymer, similar in some respects, and even closely related to, polyurethane. And, like polyurethane, it is, or can be, elastomeric, and can be produced to be cured into either solid or "foamed" products.  As can be learned via:  

Polyurea - Wikipedia, the free encyclopedia; the "Polyurea" is actually, or can be, derived from carbamic acid and it's "Carbamate Salt's", as in the above Title and Abstract; and, some of the processes for converting carbamate into Polyurea involve the re-evolution of some, but not all, of the CO2 that would, as herein, go into the initial synthesis of the "Carbamate". Our understanding is that is not the case with this University of North Dakota technology; and, all, or nearly all, of the Carbon Dioxide originally consumed in the chemical synthesis of "Carbamate" would remain forever chemically bound in the "Polyurea".)

Government Interests: This invention was made with government support under Grant No. EPS 0814442 awarded by the National Science Foundation. The government has certain rights in the invention.

Claims: A method for treating carbon dioxide, the method comprising: preparing a polyamine composition; delivering a stream containing carbon dioxide to the polyamine composition, wherein the carbon dioxide reacts with polyamine in the polyamine composition to form a carbamate salt.

The method ... wherein the stream containing carbon dioxide is a waste stream from a power plant (or) wherein the stream containing carbon dioxide is air.

The method ... wherein the polyamine composition comprises a liquid polyamine (or) wherein the polyamine is in an aqueous solution (or)wherein the polyamine is in an organic solution.

The method ... further comprising: mechanically mixing the polyamine composition while delivering the stream of carbon dioxide to the polyamine composition (and)further comprising: separating the carbamate salt from the polyamine composition (as described).

The method ... wherein the stream of carbon dioxide is delivered to the polyamine composition at a temperature between about -20 C and about 400 C.

(The temperature isn't too important, as above, with some implications for energy economy. Although we're not reproducing the specifics, the same is true of the pressures at which the Carbon Dioxide can be " delivered to the polyamine composition". They cover a broad range, again with implications for energy economy.)

The method ... further comprising: dehydrating the carbamate salt to produce a polyurea (and) wherein the method is performed in the absence of a catalyst (and) wherein the carbamate salt is dehydrated at a temperature between about 100 C and about 450 C.

(In this case, "producing a polyurea" from "the carbamate salt" shouldn't result in the re-emission of any of the captured and consumed Carbon Dioxide, as might be the case in the process described and discussed in the above article concerning Polyurea we cited and linked from the Wikipedia.)

A method for producing polyurea from carbon dioxide, the method comprising: delivering a stream containing carbon dioxide to a polyamine composition, wherein the carbon dioxide reacts with polyamine in the polyamine composition to form a carbamate salt; and dehydrating the carbamate salt to produce polyurea.

Background: Recently, efforts have been made to turn captured carbon dioxide into harmless and useful products. For example, commercially available carbon dioxide has been converted into carbonate polymers. However, this process requires a pure stream of carbon dioxide and expensive catalysts.

Summary: A method for producing polyurea from carbon dioxide includes delivering a stream of carbon dioxide to a polyamine composition. The carbon dioxide reacts with polyamine in the polyamine composition to form a carbamate salt. The method also includes dehydrating the carbamate salt to produce polyurea."

------------------------ 

The potential market for "polyurea" made from Carbon Dioxide is actually vast.

If you research the topic, you will discover that it is most often, even almost always, described in terms of being used as a "coating" or "liner" for other kinds of less durable or weaker materials, even other kinds of polymers and plastics. It is most often spray-applied, and Coal Country readers might recognize it as an aftermarket spray-on truck bed liner.

However, like polyurethane, some polyurea compositions can be molded into all sorts of various products as either a solid or foamed polymer.

One factor that has restricted it's use in molded and fabricated parts is it's cost, which historically has been significantly higher than, generally speaking, the sorts of polyurethane used in such "bulk" applications.

The molds and other equipment needed to process polyurea have also historically required higher performance standards than for polyurethane, as well.

But, if we could, as herein, start making polyurea from our, some say too abundant, domestic Carbon Dioxide, instead of imported OPEC petrochemicals, that extra equipment expense, relative to the improved property advantages offered by polyurea, might seem fairly minor. And, the resulting market for CO2-based polyurea could, again, prove to be vast.

In any case, we have herein again more evidence of the fact, that: Carbon Dioxide, as it is co-produced by our use of Coal in the generation of reliable and affordable electric power, could be seen and treated as a valuable raw material resource, a resource which would offer the potential of new manufacturing industries and increased employment in United States Coal Country.

And, again herein, that is a fact that "public officials" in the employ of our United States Government, in the United States Patent and Trademark Office, aren't making any attempt "to keep secret", which, as seen in: 

We’re The Real Public Servants - News, Sports, Jobs - The Intelligencer / Wheeling News-Register; "'We’re The Real Public Servants'; March 23, 2014; The Intelligencer / Wheeling News-Register; It has never been easy to pry information public officials want to keep secret out of their hands. But I've been a newspaperman for more than 40 years - and I don't ever recall it being as difficult as it is now. Last week, many of us in the press observed "Sunshine Week" in various ways. The idea was to inform you, our readers, about government threats to your right to know";

perhaps isn't always the case regarding other issues that some might see as important. But, the fact that Carbon Dioxide can be used and consumed so productively, as in the process of our subject, "US Patent Application 20140024800 - CO2  Capture and Conversion to a Carbamate Salt and Polyurea", is, we would think, one of some importance to those US citizens living and working, or attempting to find work, in US Coal Country, with the current basis of their economy threatened as it is by predations like Cap and Trade Carbon taxation; and, with too much of their earnings, whatever those earnings might be, consumed in the purchase of imported OPEC hydrocarbons, whether in the form of fuel or plastics.

Maybe our Coal Country press corps, our self-proclaimed "Real Public Servants", need to declare a new "Sunshine Week"; and, to apply it's principles this time around to themselves, as well.