New Jersey Consumes CO2 in the Synthesis of Polymers

United States Patent: 8691069

Friends, we're coming down to it here.

Either you care about the United States of America - her people and her ideals - or, you don't.

Either you care about the present and future security of your own children, or, you don't.

Either you care about the Truth, or, you don't.

 

Quite obviously to us, here, in our little enclave of volunteer miners of information, as became apparent, tragically, to us on a directly personal level some time ago: nobody - at least it seems - does care, not really, not, at least, about much of anything genuinely related to justice and honor and truth.

Here's the deal: If you've paid any attention at all to our thousands of little love notes over the past half dozen years, either as you've received them directly from us or as you've read them as they've been responsibly posted on the web by the West Virginia Coal Association, you will know what should be a couple of dazzling facts, maybe so dazzling they're too painful to contemplate relative to the way you, all of us, have been and are being victimized by those who benefit from the status quo, i.e.:

Coal, the very economic bedrock of West Virginia and some other similarly blessed states, can be, as it is being in some other nations of the world, efficiently converted into anything and everything, that is, synthetic petroleum and hydrocarbon fuels, we've been allowed, even encouraged, to continue squandering our national and personal wealth to buy from the completely, in terms of ideals and outlook, foreign nations of OPEC.

And:

Carbon Dioxide, too, the very thing some folks genuinely concerned about the environment, and some other folks not concerned with much of anything at all except lining their own pockets, want to tax our vital Coal-fired power generation industries out of existence for co-producing along with abundant and affordable electricity, can be efficiently reclaimed and then consumed in the synthesis of both liquid and gaseous hydrocarbon fuels and in the synthesis of chemical raw material for manufacturing plastics and polymers.

Those are the facts. But, nobody, it seems, cares.

Now, if you disagree, if you do care, then you need now to get off your dead cans and find some way to take action. You need to prove, and now, that you do care.

We'll suggest some ways to go about that further on - - after treating our subject today, another example of technology demonstrating yet again that Carbon Dioxide, as it arises in only a very small way, relative to some all-natural and un-taxable sources of it's emission, such as the Earth's inexorable and global processes of planetary volcanism, from our economically and strategically essential use of Coal in the generation of abundant and affordable electricity, is a valuable raw material resource.

As we've seen for one example in:

Bayer Is Converting Coal Power Plant CO2 Into Plastics | Research & Development | News; concerning:

"'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. ...
Bayer aims to use CO2 as an alternative to production of polymer materials from   fossil fuels.

Carbon Dioxide can be, and in fact is being, used as a raw material, in place of feed stock conventionally derived from petroleum, for the synthesis of certain high-value, high-performance and high-volume plastics and polymers.

As we've further seen, most recently, for just one example, in our report of:

Princeton University March, 2014, CO2 to Methanol | Research & Development | News; concerning: "United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products; Date: March 4, 2014; Inventors: Andrew Bocarsly, NJ, and Emily Barton Cole, TX; Assignee: Princeton University, NJ; Abstract: 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 ... to produce therein a reduced organic product. Government Interests: This invention was made with United States government support from National Science Foundation Grant No. CHE-0616475. The United States Government has certain rights in this invention. Claims: An environmentally beneficial method of producing methanol by electrochemical reduction of any available source of carbon dioxide";

our United States government has been funding the development, at Princeton University, of technology whereby CO2 can be consumed in the synthesis of, among other things, fuel alcohol Methanol.

The rather immense value and utility of Methanol for the time aside, we've also seen, for one example in: 

New Jersey May 21, 2013, CO2 to Plastics Raw Materials | Research & Development | News; concerning: "United States Patent 8,444,844 - Electrochemical Co-production of a Glycol and an Alkene Employing Recycled Halide; May 21, 2013; Inventors: Kyle Teamey, DC, Jerry Kaczur, FL, and Emily Barton Cole, TX; Assignee: Liquid Light, Inc., NJ; Abstract: The present disclosure is a method and system for electrochemically co-producing a first product and a second product (which) may include co-producing a glycol and an alkene employing a recycled halide. Claims: A method for co-producing a first product and a second product, the method comprising the steps of: contacting a first region of a first electrochemical cell having an cathode with a catholyte comprising carbon dioxide (and further steps as disclosed) The method ...  wherein at least one of glyoxylic acid, glyoxal, glycolic acid, glycolaldehyde, acetic acid, acetaldehyde, ethanol, ethane, ethylene, or ethylene glycol is recoverable from the first region of the second electrochemical cell";

how a company, "Liquid Light Incorporated", of New Jersey, described by some references as a commercial "spin-off" off Princeton University, created to commercialize and further develop the Carbon Dioxide utilization technologies invented in the Princeton labs of Professor Andrew Bocarsly, lead named inventor of "United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products", as cited above,.has been developing technology wherein Carbon Dioxide can be consumed in the synthesis of more fuel alcohol, "ethanol", and of products like "ethylene glycol".

Ethylene Glycol is a product of rather unique value, since, as can be learned via:

Ethylene glycol - Wikipedia, the free encyclopedia;

it is a preferred raw material for the further synthesis of polyester and of polyethylene terephthalate resins, which are ubiquitous plastics used in the manufacture of high-volume products like synthetic fibers and plastic bottles; and, in which plastics the Carbon Dioxide consumed in the synthesis of the Ethylene Glycol would remain, chemically and permanently, and productively, "sequestered".

And, herein we learn that technical experts in the employ of our United States government quite recently confirmed that Liquid Light, Inc., has developed even additional technology for the efficient utilization and consumption of Carbon Dioxide in the synthesis of, really, a rather startling range of intermediate products which can be further processed, in some cases via reaction with even more products derived from Carbon Dioxide, and made finally to form both polymer raw materials and fuels.

It is rather immensely complicated, and our exposition of it all will leave much to be desired. We'll do our best; and, hopefully that will be enough to motivate someone qualified and genuinely concerned about issues like the Cap and Trade CO2 tax threat to our economically vital Coal-use industries, and like the potentials for United States self sufficiency in her supply of liquid and gaseous hydrocarbon fuels and in her supply of petrochemicals used as raw materials in the plastics and polymers industries - - and the vast positive economic implications all of that could have for all of us living and working in United States Coal Country, to go ask the good folks at Liquid Light all about and then bring full and cogent report of it all back home to us.

As unlikely as such now seems to be, we'll keep swinging, and, thus, comment follows and is inserted within excerpts from the initial link in this dispatch to the very recent:

"United States Patent 8,691,069 - Method and System for the Electrochemical Co-Production of Halogen and Carbon Monoxide for Carbonylated Products

Method and system for the electrochemical co-production of halogen and carbon monoxide for carbonylated products - Liquid Ligh

April 8, 2014

Inventors: Kyle Teamey, et. al., DC, FL and TX

Assignee: Liquid Light, Inc., NJ

Abstract: The present disclosure is a system and method for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode. The method may include a step of contacting the first region with a catholyte including carbon dioxide and contacting the second region with an anolyte including a recycled reactant. The method may further include applying an electrical potential between the anode and the cathode sufficient to produce carbon monoxide recoverable from the first region and a halogen recoverable from the second region.

Claims: A method for co-producing carbon monoxide from a first region of an electrochemical cell having a cathode and a halogen from a second region of the electrochemical cell having an anode, the method comprising the steps of: contacting the first region of the electrochemical cell with a catholyte comprising carbon dioxide; contacting the second region of the electrochemical cell with an anolyte comprising a recycled reactant, wherein the recycled reactant is HX, where X is selected from the group consisting of Flourine, Chlorine, Bromine, and Iodine; and applying an electrical potential between the anode and the cathode of the electrochemical cell sufficient to reduce the carbon dioxide and co-produce the carbon monoxide recoverable from the first region of the electrochemical cell and the halogen recoverable from the second region of the electrochemical cell (and) wherein the halogen includes at least one of Fluorine, Chlorine, Bromine or Iodine. 

The method ... further comprising: drying the carbon monoxide recovered from the first region and the halogen recovered from the second region (as specified, and) reacting the carbon monoxide recovered from the first region, the halogen recovered from the second region and an additional reactant to form a third product and the recycled reactant. 

(It can get a tad interesting here, as we'll see. The "halogen" and the "carbon monoxide" can both be used and consumed in the synthesis of high-volume polymers, in ways which enable the consumption of even more products which can be, and are being, synthesized from Carbon Dioxide.)

The method ... wherein the additional reactant includes at least one of an amine, ... , or at least one of an alcohol, methanol, and ethanol, and mixtures thereof.

(Note that "methanol" is one of the products that can be reacted, "carbonylated" with the Carbon Monoxide extracted herein from Carbon Dioxide; and, we remind you, that, in addition to our above-cited report concerning: "US Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products; ... An environmentally beneficial method of producing methanol by electrochemical reduction of any available source of carbon dioxide"; as seen previously in our report of:

CO2-to-Methanol Supported by World's Largest Methanol Supplier | Research & Development | News; concerning the news release: "'Methanex and Carbon Recycling International Sign Landmark Investment Agreement for Advanced Renewable Fuel Production'; July 30, 2013; REYKJAVIK, ICELAND - Methanex Corporation ... announced today an initial $5 million investment in Carbon Recycling International (CRI), a privately held company with headquarters in Reykjavik, Iceland. Methanex will also evaluate further investments to support CRI's growth. CRI operates the world's first renewable methanol plant in Iceland which utilizes its emissions-to- liquids (ETL) technology, converting renewable energy and recycled CO2 emissions to renewable methanol. ... CRI markets its renewable methanol in Europe, under the registered brand name Vulcanol, where it is blended with gasoline";

the synthesis of the needed Methanol from Carbon Dioxide, to be reacted herein with Carbon Monoxide extracted from Carbon Dioxide, is already a commercial, industrial reality, although it is being accomplished through the utilization of technology significantly different than that disclosed by Princeton University in their "US Patent 8,663,447". 

Further, "ethanol" is another alcohol which can, as herein, be reacted with the Carbon Monoxide extracted from Carbon Dioxide. And, as seen in our report of:

Princeton University November 20, 2012 CO2 to Ethanol | Research & Development | News; concerning:

"United States Patent 8,313,634 - Conversion of Carbon Dioxide to Organic Products; 2012; Inventors: Andrew Bocarsly and Emily Barton Cole, NJ; Assignee: Princeton University, NJ; Abstract: 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 ... to produce therein a reduced organic product. Government Interests: This invention was made with United States government support from National Science Foundation Grant No. CHE-0616475. The United States Government has certain rights in this invention. Claims: A method of converting carbon dioxide to provide at least one product selected from the group consisting of glyoxal, isopropanol, ethanol";

Princeton University, in the persons of Andrew Bocarsly and Emily Cole, have established the technology for accomplishing the transmutation of Carbon Dioxide into that needed Ethanol, as well. And, also keep in mind, that, as can be learned separately via:

"United States Patent: 4138440 - Conversion of Liquid Alcohols ... with ... ZSM-5 Type Catalyst; 1979; Mobil Oil Corporation; Abstract: The conversion of alcohols ... to gasoline ... with HZSM-5 catalyst. Claims: A method for converting ... methanol, ethanol ... and mixtures of alcohols and ethers to gasoline";

both Methanol and Ethanol, as perhaps synthesized from Carbon Dioxide via processes disclosed by Princeton University and/or Liquid Light, Incorporated, can be, via known processes, converted directly into Gasoline.)

The method ... wherein the third product includes one of isocyanate, methyl isocyanate, butyl isocyanate, phenyl isocyanate, diisocyanate, methylene-diphenylisocyanate, phenyl-diisocyanate, hexamethylene-diisocyanate, toluene-diisocyanate (and, etc.).

(And, here it might get especially interesting. By reacting Carbon Monoxide, which was extracted as herein  from Carbon Dioxide, with Methanol/Ethanol, which can as well be made from Carbon Dioxide, we can make an "isocyanate" of one sort and another. And, as can be learned separately via:

Bayer MaterialScience NAFTA - Our Businesses - Polyurethane Systems and Raw Materials - What is Polyurethane?; “Polyurethanes are formed when a polyol reacts with a diisocyanate or a polymeric isocyanate when there are suitable catalysts and additives present“;

"Polyurethanes", which are a class, or type, of polymers with an absolutely vast array of properties with suitability for, thus, a vast array of applications, and which are consequently in huge demand, are typically made by reacting "isocyanate" - - as can be made via the process of our subject herein, "United States Patent 8,691,069 - Method and System for the Electrochemical Co-Production of Halogen and Carbon Monoxide for Carbonylated Products", from Carbon Dioxide - - with a "polyol". And, as can be seen in:

"United States Patent: 4230824 - Sucrose Based Polyether Polyols; 1980; Inventor: Neil Nodelman, New Martinsville, WV; Assignee: Mobay Chemical Corporation (now Bayer Corporation); Pittsburgh, PA; Abstract: The invention provides a means for making ... sucrose-based polyether polyol"; and:

Natural oil polyols - Wikipedia, the free encyclopedia;

such "polyol"s can be made from naturally Carbon-recycling botanical sugars and/or botanical oils.)

The method ... further comprising: reacting the halogen recovered from the second region and an additional reactant to form a third product and the recycled reactant (and) wherein the additional reactant is a halocarbon and the third product is a dihalogenated hydrocarbon (and which method) further comprising: converting the dihalogenated hydrocarbon to acetylene and the recycled reactant via a dehydrohalogenation reaction (and, which ,method) further comprising: reacting the carbon monoxide recovered from the first region, acetylene, and one of water or alcohol to form one of acrylic acid or acrylic acid esters.

(Note the additional products which can be derived herein from Carbon Dioxide, i.e., "acetylene"; and, "acrylic acid esters" - which are valuable in the synthesis of acrylic polymers.) 

The method ... wherein the cathode and the anode are separated by an ion permeable barrier (and) wherein the ion permeable barrier includes one of a polymeric or inorganic ceramic-based ion permeable barrier. 

The method ... wherein the catholyte is liquid phase and the anolyte is gas phase (and) wherein the liquid phase of the catholyte liquid phase is an aqueous solution including an electrolyte including one or more of alkali metal sulfates, carbonates, chlorides, phosphates, borates, nitrates, and nitrites.

The method ... wherein the catholyte further includes a homogeneous catalyst (selected from) unsubstituted pyrimindine, substituted pyridine, (etc.).

Background and Field: The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical co-production of halogen and carbon monoxide for use in carbonylation reactions. 

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.

Summary: 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."

-------------------------- 

Extended discussion goes into some of the details about how the industrially and economically important isocyanates can be/are made via reactions between the CO2-derived Carbon Monoxide and the "halogen", which is pretty much how isocyanates are made in any case, through the intermediate production of phosgene, which is a pretty nasty substance, actually a "mustard gas", but, which is consumed in the isocyanate synthesis - - and which is pretty much how it's done in major polyurethane raw material manufacturing facilities in any case. It is an understood and widely-practiced process.

In most cases, the "halogen" is Chlorine, as extracted from the salts in fossil deposits of brine, a lot of which are found, for instance, under the state of West Virginia, and which have been the bases of a number of chemical industries there.

In sum, we have herein further confirmation by our United States Government, through their issuance and allowance of our subject, "United States Patent 8,691,069 - Method and System for the Electrochemical Co-Production of Halogen and Carbon Monoxide for Carbonylated Products", of the fact, that:

Carbon Dioxide, as it is co-produced in 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 economically essential use of Coal in the generation of truly abundant and truly affordable electric power is a valuable, maybe even a precious, raw material resource.

Carbon Dioxide can be reclaimed from whatever handy source, and then be consumed as a raw material, in place of raw materials conventionally derived from OPEC petroleum, in the synthesis of high performance and high volume plastics and polymers, wherein the reclaimed Carbon Dioxide would remain forever chemically, and productively and profitably, "sequestered".

Now, returning to our introductory comments, far above. We don't want to name names, since the realization began to dawn on us years ago that we, here, don't really have nearly as many friends as we once thought we had - if, in fact, we have any at all; and, honestly, we few lonely souls in our isolated little outpost can't afford to make any more enemies than those, both obvious and less-obvious, than we already do have.

So, we won't name names, but, these "Coal R&D" reports are directed primarily to a small group of Coal Country journalists; news people, in other words, whom one would have thought to have interest in issues such as we treat, which issues could be directly related to the prosperity and to the futures of the Coal Country communities those journalists present themselves as serving.

Now, nothing, insofar as we know, has appeared in the Coal Country media concerning the very real prospects for the technologies we have devoted the bulk of our reports to exposing, that is, the conversion of Coal into anything and everything we're now giving away the farm to buy from OPEC and, as herein, the productive recycling of Carbon Dioxide, which some folks want to tax our vital Coal-fired power generation industry out of existence for co-producing a little of, into the same sorts of things.

Again, we can't name names, since we already perceive a certain amount of passive hostility directed towards our vulnerable selves, and we can't afford to have the passive become aggressive.

But, here's what you can do. The following link:

http://wvpress.org/wvnewspapers/;

will take you to, on the West Virginia Press Association's web site, their list of member WV news publications. Many, perhaps most, of those publications have web site links of their own.

Now, presuming you to be fairly computer and inter net savvy, since you found this report tucked away in the "R&D" slot of the West Virginia Coal Association's web site in the first place, here's what you can do while you're waiting on dinner or the next rerun of Burn Notice:

Log onto the web sites of at least a few of those West Virginia news publications that have them, and, on those web sites, track down either their "Comments" utility or, better, the email addresses of the publisher and/or editor, or at least a reporter or two.

Write them a brief email or comment utility note telling them that Coal can be converted into Gasoline and that Carbon Dioxide can, as seen herein, be consumed in the making of plastics, tell them where you saw those facts demonstrated, and, if you can, send them a link, either to this article, or, as via:  

http://www.wvcoal.com/table/news/research-development/;

to the whole shebang.

And, tell them, politely, that you sure would like to see the subject treated fully, openly, publicly and professionally in a West Virginia newspaper - - that you can't understand why it hasn't already been so treated since it has such seemingly great potentials for West Virginia jobs and such.

And, maybe you could ask your buddies in the dinner hole or the bath house to do the same thing.

Now, we know that's a little bit of extra work, but, we're talking about the economic, and military, security of the United States of America here, and the future well being of your children and grandchildren, so we don't think that, in the grand scheme of things, it's really a lot to ask.

Do you?

We, here, for what it's worth, are interested in finding out.