http://www.arkat-usa.org/get-
As we recently reported, via:
West Virginia Coal Association | Taiwan Converts CO2 into Plastics Raw Material | Research & Development; concerning: "US Patent Application 20130035497 - Manufacturing Cyclic Carbonate from Carbon Dioxide; 2013; Inventor: Shiey-Shiun Horng, Taiwan; (presumed eventual Assignee of Rights: I-Shou University, Taiwan); Abstract: A method of manufacturing cyclic carbonate with carbon dioxide including the steps of placing solid catalyst in a reaction tube, vaporizing epoxide molecules within a buffer tank to obtain an epoxide vapor, and injecting carbon dioxide into the buffer tank. The carbon dioxide mixes with the epoxide vapor in the buffer tank to obtain an air mixture. The air mixture is then conducted into the reaction tube, where catalysis by the solid catalyst generates cyclic carbonate";
wherein the product, "cyclic carbonate", can be utilized as, among other things, a molecular chemical building block for various and specific types of plastic, there are advances being made in the productive consumption and permanent use of Carbon Dioxide, above and beyond those CO2-recycling technologies typified by our report of:
West Virginia Coal Association | Iceland, August 2012, CO2 to Gasoline and Diesel | Research & Development; concerning: "US Patent Application 20120201717 - Process and System for Producing Liquid Fuel from CO2 and Water; 2012; Assignee: CRI, Iceland; Abstract: A process and system for producing high octane fuel from carbon dioxide and water is disclosed. The feedstock for the production line is industrial carbon dioxide and water, which may be of lower quality. The end product can be high octane gasoline, high cetane diesel or other liquid hydrocarbon mixtures suitable for driving conventional combustion engines";
wherein Carbon Dioxide is simply recycled back into "liquid fuel", such as "high octane gasoline", which, upon combustion, would return the CO2 to the atmosphere.
We note without reference that there have been of late some strident voices being raised in England, and elsewhere, denying the reality of CO2-based climate change; and/or claiming, that, if CO2 does contribute to so-called global warming, that wouldn't necessarily be a bad thing; more crops could be grown during longer seasons, with the crop growth enhanced by elevated levels of CO2, which green plants consume and convert into botanical products through photosynthesis.
Our take is that those are debates which will rage on, unresolved, for centuries among those with little better to do than satisfy their peculiar needs to bicker across the dinner table.
Our further take is that it's far past time we just got our fannies into gear, filled our jugs up with coffee and headed off to do some real work.
And, in England, there are apparently some folks who do feel the same way.
In addition to those academic laborers at the University of Oxford, who, as we reported in:
West Virginia Coal Association | The University of Oxford Converts CO2 into Methanol | Research & Development; concerning, in part: "Process For Producing Methanol; Publication No: WO/2011/045605; International Application No: PCT/GB2010/051733; 2010; Inventors: Dermot O'hare and Andrew Ashley, Great Britain; Applicants: Isis Innovation Limited, Great Britain (Isis Innovation Ltd is a British technology transfer company, wholly owned by the University of Oxford); Abstract: The present invention relates to a novel process for the production of methanol ... by ... the hydrogenation of CO2";
have devised innovative technology for converting CO2 into fuel alcohol, other British scholars have followed the path defined in our above-cited report of "US Patent Application 20130035497 - Manufacturing Cyclic Carbonate from Carbon Dioxide", and further defined the ways by which CO2 can be consumed in the synthesis of just such raw materials for the manufacture of plastics.
As seen in excerpts from the initial link in this dispatch to:
"'Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide Using Bimetallic Aluminum Complexes’”
by Michael North
School of Chemistry, University of Newcastle; Newcastle upon Tyne, UK
Abstract: Over the last six years, highly active catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide have been developed. Initial studies showed that bimetallic aluminium(salen) complexes [Al(salen)]2O formed active catalysts and kinetic studies allowed the catalytic cycle to be determined. The catalysts could be immobilized on silica, allowing them to be used in a gas phase flow reactor as well as in batch reactors. The compatibility of the catalysts with waste carbon dioxide present in power station flue gas has been investigated and studies to enhance the commercial applicability of the catalysts by reducing the cost of their production carried out.
The world currently generates most of its energy by the combustion of fossil fuels (coal, oil and natural gas) and despite efforts to develop alternative, renewable energy sources, fossil fuels are likely to remain the predominant energy source for the next 20–40 years. Combustion of fossil fuels inevitably produces carbon dioxide which is released to the atmosphere.
The main solution being proposed to allow continued energy generation by combustion of fossil fuels whilst stabilizing global atmospheric carbon dioxide levels is carbon capture and storage (CCS) in which the carbon dioxide is separated, purified, pressurized and transported for long term underground or undersea storage. However, CCS is a very energy intensive process which has been estimated to require around 30% of the total energy produced by a power station.
(We've previously documented that level of energy expenditure for "CCS". Can we really afford such unwarranted extravagance?)
Instead of just dumping the carbon dioxide, it is attractive to consider utilizing it in the large scale production of chemicals (carbon capture and utilization, CCU). In this way, an unwanted waste product can be turned into a valuable commodity. The relative scales of production of energy and chemicals inevitably means that only a relatively small amount of carbon dioxide could be recycled through CCU, but this could be a very profitable undertaking and could be used to partially offset the costs associated with CCS for the remaining carbon dioxide.
(We disagree with the above statement, that "only a relatively small amount of carbon dioxide could be recycled". Technologies exist, as we will more fully document in the future, to convert waste Carbon Dioxide into "bulk" construction and building products, wherein far larger amounts of CO2 would be permanently "sequestered". Further, the CO2 emissions avoided by not having to extract, transport, and process raw materials made redundant by the recycling of CO2 must be entered into the equation. For instance, as disclosed in our above-cited report concerning "US Patent Application 20120201717 - Process and System for Producing Liquid Fuel from CO2 and Water; 2012; Assignee: CRI, Iceland; Abstract: A process and system for producing high octane fuel from carbon dioxide and water is disclosed. The feedstock for the production line is industrial carbon dioxide and water, which may be of lower quality. The end product can be high octane gasoline, high cetane diesel", if we can make the stuff we import from OPEC out of Carbon Dioxide, what quantity of CO2 emissions would thus be avoided by not having so many Oil tankers plying the seas back and forth, and by not having to send massive military missions to the Middle East and Arabia, all powered at least in part by internal combustion and jet or turbine engines, on what seems such a regular basis?)
Clearly, for CCU to be effective the energy requirements of the process should be very low (or the process should be linked to renewable energy), otherwise more carbon dioxide will be generated producing the required energy than is utilized in the chemical production.
(And, as seen for only one example in:
West Virginia Coal Association | Japan Solar Energy Converts More CO2 into Methane | Research & Development; concerning: "United States Patent Application 20120234691 - Method for Reducing Carbon Dioxide; 2012; Panasonic Corporation; Abstract: The method for reducing carbon dioxide of the present disclosure (uses an) electrochemical cell ... capable of reducing carbon dioxide at an overvoltage equal to or lower than overvoltages for conventional catalysts for reducing carbon dioxide. Therefore, the method of the present disclosure makes it possible to produce highly useful substances, such as HCOOH, CH4, C2H4 and C2H6, at an overvoltage equal to or lower than overvoltages in conventional methods. ... The method for reducing CO2 of the present disclosure can be applied to methods using a solar cell as an external power supply. The catalyst for reducing CO2 can be applied, by combination with a photocatalyst, to catalysts which can be used with solar energy";
there has been a great deal of success achieved in the development of catalysts that convert CO2 into such things as Methane, "CH4", at voltages, at energy requirements, that are so low such CO2-recycling processes can be powered by "solar", i.e., as our subject specifies, "renewable", "energy".)
(Recently) Carbon Recycling International opened the first commercial scale plant for the direct reduction of carbon dioxide to methanol using geothermal energy to produce the required hydrogen from sea water.
(As in our above citation of our report concerning "US Patent Application 20120201717 - Process and System for Producing Liquid Fuel from CO2 and Water; 2012; Assignee: CRI, Iceland; Abstract: A process and system for producing high octane fuel from carbon dioxide and water is disclosed". See also, for another example, our report of:
West Virginia Coal Association | Iceland Recycles Even More CO2 | Research & Development; wherein we're told, in part: "Carbon Recycling International (CRI) captures carbon dioxide from industrial emissions and converts carbon dioxide into Renewable Methanol (RM). RM is a clean fuel and can be blended at different levels with gasoline to meet renewable energy directives. The capture of carbon dioxide minimizes emissions from energy intensive industries. It is compatible to the existing energy and fuel infrastructure.")
Another well-known reaction of carbon dioxide is its reaction with epoxides which can be controlled to form either cyclic carbonates or polycarbonates. Polycarbonate production in this way is currently being commercialized in the UK, Germany, USA and South Korea. The synthesis of cyclic carbonates from epoxides and carbon dioxide has been a commercial process since the 1950s and is now operated commercially by many different companies worldwide.
(The above is as exemplified by our report, already noted, with more, similar, to follow, of "US Patent Application 20130035497 - Manufacturing Cyclic Carbonate from Carbon Dioxide". These scientists from the University of New Castle then go into some detail concerning the needed "Salen" complexes, about which we've previously reported, but danged if we can find the specific reference right now. In any case, as can be learned via:
Metal salen complexes - Wikipedia, the free encyclopedia; "Salens are a class of organic compounds used as ligands in coordination chemistry"; and:
Salen ligand - Wikipedia, the free encyclopedia; "Salen is the abbreviation for a popular chelating ligand used in coordination chemistry and homogenous catalysis"; and:
Ligand - Wikipedia, the free encyclopedia, and: Coordination complex - Wikipedia, the free encyclopedia;
such stuff is, by people specifically educated in the matter, well-known, well-understood and utilized.
You don't understand "Salens", and neither do we; but, there are people who do, people who could help us put them to work recycling, as herein, Carbon Dioxide.)
It is highly desirable that new technologies developed to utilize carbon dioxide as part of a CCU system are compatible with carbon dioxide at the concentrations, pressures and purities at which it is readily available as waste. In this way all of the costs (financial and energy) associated with purifying, concentrating and pressurizing the waste carbon dioxide can be avoided. Waste carbon dioxide is produced with many different purities, but the largest scale and least pure form is the carbon dioxide present in the flue–gases of a fossil fuel power station which typically has a concentration of 6 -13% carbon dioxide and contains numerous other impurities including water vapor, nitrogen oxides and sulfur oxides.
Since flue–gas is not commercially available and cannot be bottled, we investigated the use of simulated flue–gas as a carbon dioxide source for cyclic carbonate synthesis using silica supported catalyst in the gas–phase flow reactor.
(Not reflected in our excerpts, due to length and complexity, is their rather detailed description of just such a "gas-phase flow reactor". They know exactly how to build one.)
The carbon dioxide concentration was chosen so that after addition of epoxide, the concentration of carbon dioxide in the gas stream entering the flow reactor would be 16% which is close to the upper limit for carbon dioxide present in flue–gas. (As shown,) the effect of 12 days continuous operation of the flow reactor with either pure carbon dioxide in nitrogen or simulated flue gas using either ethylene oxide or propylene oxide as substrate. It is apparent that the nitrogen and sulfur oxides present in the simulated flue gas had no detrimental effect on the catalyst activity, lifetime or ability to be reactivated.
(They go on to note that some Sulfur compounds which might be present in power plant flue gas do tend to impair catalyst activity, but, that, the rate of catalyst deactivation is so slow that you could likely get a year's worth of work out of them before they might need to be changed or processed for reactivation. Other catalyst candidates were tested which indicated even longer lives could be achieved. But, tests in real Coal power plant flue gas indicated the need for ash precipitation/removal prior to passing the flue gas into the Carbon Dioxide conversion reactor. We regret our need to summarize so much; but the University of Newcastle's presentation is accompanied by explanatory illustrations, diagrams and equations which we are unable to excerpt for you.)
Catalyst Cost Reduction: Most aspects of the synthesis of cyclic carbonates using bimetallic aluminium complexes are either unchanged from the current commercial process (e.g. amount of epoxide required), or are self evidently less costly (no need for high pressures and temperatures). The one exception is the cost of the catalyst itself. Therefore a study was undertaken specifically to minimize the cost of production of the catalyst.
(They then explain and describe their study of catalyst cost, with the upshot being that they devised a combination of them that seems both affordable enough and durable enough to be practical.)
Conclusions: This work has resulted in the development of a class of bimetallic, aluminium based catalysts for the synthesis of cyclic carbonates (including all the commercially important cyclic carbonates) which are active under exceptionally mild reaction conditions. Batch reactions can be carried out at ambient temperature and one bar carbon dioxide pressure whilst continuous flow reactions can be carried out at 100 oC using catalysts immobilized on amorphous silica.
The catalysts have been shown to be compatible with waste carbon dioxide such as that present in unpurified flue-gas.
The cost of production of the catalysts has been analyzed and routes for their synthesis developed to minimize the cost of their production.
The intellectual property associated with this work is protected by three patent families and a spin-out company (Dymeryx Ltd.) has been established to commercialize the technology.
The project provides an excellent illustration of how carbon capture and utilization can provide a sustainable feedstock for use by the global chemicals industry in the 21st century."
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A little more information is available via:
Enterprise - Research and Enterprise Services - Newcastle University; "New Castle University 'spin outs', 2010: Dymeryx Ltd will develop and exploit speciality catalysts and associated chemical process designs. It is focused on developing novel processes to utilise waste carbon dioxide as an industrial feedstock. Founder: Professor M North"; although the Dymeryx web site itself is still being developed, New Castle University has another web-based home for their "spin outs":
synthesis of dimethyl carbonate from waste CO2 | Innovate 10; "Dymeryx has unique technology which enables waste CO2 from flue gas to be converted into commercially important ethylene carbonate without the need for any purification of the flue gas."
And, one further note: We have now documented via several reports that Carbon Dioxide can be reacted with the natural epoxide, "limonene", or "limonene oxide", which is, as the name implies, derived from citrus fruit, to make "cyclic carbonates" and, ultimately "polycarbonates" and other quite valuable plastics, wherein any of the CO2 originally consumed would be permanently, and productively and profitably, "sequestered".
The immediate inference should be, of course, that "limonene", originating as it does from a botanical source, already represents a certain amount of naturally recycled Carbon Dioxide, so the CO2 reduction effect of the process is multiplied.
And, we wanted to make certain that it was understood that "limonene" is not the only suitable plant oil which can be used in such reactions. Limonene is, in the general sense, a "terpene", and, yes, that is where we get the word "turpentine". So, any old country boy will know that we have some "terpenes" available to us in US Coal Country; and, in a conference whose full agenda should be closely studied by anyone with a genuine interest in CO2 issues and how they could beneficially impact our Coal Country lives:
http://www.co2-chemistry.eu/
we find separate presentation of:
"Carbonates and Polycarbonates from Plant Terpenes and CO2", a report of similar developments made in Germany.
Again, keeping in mind that plant terpenes, like Limonene, already represent a certain amount of naturally recycled CO2; consider that, as confirmed herein by the United Kingdom's University of New Castle, we can react such CO2-recycling plant oils with "waste carbon dioxide such as that present in unpurified flue-gas", and thereby synthesize "cyclic carbonates", valuable in the synthesis of a number of plastics, "or polycarbonates":
Polycarbonate - Wikipedia, the free encyclopedia;
which is a broad class of plastic materials with a presence in each and everyone of our daily lives, and which represents a truly vast potential for the permanent, and immensely beneficial, consumption of that valuable raw material resource, that "sustainable feedstock", Carbon Dioxide.