CO2 as New Carbon Source for Chemical Industry | chemanager-online.com - Chemistry and Life Science
In a few recent reports, now accessible via:
West Virginia Coal Association | Bayer Corporation Promotes Carbon Dioxide Recycling | Research & Development; concerning: "The Bayer Scientific Magazine; 'Three Atoms for a Clean Future'; CO2 destined to become a valuable raw material for innovative substances; Together with a group of partners, Bayer researchers are making good progress in this direction, and have found a way to incorporate CO2 into the molecular structure of polyurethanes, thus saving oil"; and:
West Virginia Coal Association | Bayer Is Converting Coal Power Plant CO2 Into Plastics | Research & Development; 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";
and in some others, related, of a more technical nature, we documented the fact that Bayer, a monument among the international chemicals and technology business community, and a major corporate citizen in certain parts of US Coal Country, has not only developed technologies which enable the productive chemical recycling of Carbon Dioxide, but, has reduced those technologies to at least pilot-scale industrial practice using CO2 captured from an honest-to-Goodness Coal-fired power plant.
Herein, we submit a little more recent summary description of that Bayer enterprise, as excerpted from the initial link in this dispatch, with comment inserted and appended:
"CO2 as New Carbon Source for Chemical Industry
March 27, 2012
Hidden Value - If one thinks about coal-fired power plants, what is it that comes first into one's mind?
The picture of high-value starting materials or rather the picture of low value carbon dioxide (CO2) emissions?
Most people will probably end up with the latter one. However, the utilization of CO2 as a valuable raw material is not as devious as one would expect: Advanced research shows that it could be used as new source of carbon - thus replacing at least partially crude oil from which the element is normally extracted.
(If the English usage seems a little "off", keep in mind that this was either translated from a European language, probably German; or, written in English in the first place by a someone for whom English is not their first tongue.)
At present, the chemical industry is mainly dependent on petroleum, both as a feedstock and energy source (as) roughly 6-7% of the annual oil production is consumed by this sector. To become more independent in terms of energy, renewable resources and energy storage options are a matter of current research all over the industry.
Replacing petroleum as product feedstock is also part of the ongoing research. The chemical industry is looking for realistic alternatives, for example biomass, coal or gas. ... How about CO2?
In the chemical literature, researchers have been discussing for decades to use carbon dioxide directly as a chemical feedstock. All over the world, attempts to make use of this waste product have emerged in regular cycles. Currently, there are various research activities dealing with the utilization of CO2 as chemical building block. In Germany for example, the Federal Ministry of Education and Research (BMBF) is heavily investing into this research area.
But there is one technical obstacle that makes this appealing idea very challenging: the low energetic level of CO2. No matter what product one strives for, it will always be necessary to invest huge amounts of energy to enable a reaction with CO2.
Consequently, new CO2 emissions will be the result.
(The implication of the above being, that, we would have to generate energy to use in forcing CO2 to become involved in chemical reactions; and, the generation of that energy would be done in a way, like burning fossil fuel to generate electricity, which would also generate more CO2. Which implication ignores that facts, that, as seen, for just two examples, in:
West Virginia Coal Association | USDOE Recycles CO2 to Methanol with Solar Power | Research & Development; concerning: "United States Patent 6,066,187 - Solar Reduction of CO2; 2000; This invention was made with government support ... (from) the U.S. Department of Energy to The Regents of the University of California. The government has certain rights in the invention. Abstract: The red shift of the absorption spectrum of CO2 with increasing temperature permits the use of sunlight to photolyze CO2 to CO (and)excess thermal energy may be used to produce electricity and to heat additional CO2 for subsequent process steps. The product CO may be used to ... synthesize methanol"; and, in:
West Virginia Coal Association | Penn State Designs CO2-to-Methane Bioreactor | Research & Development; concerning: "United States Patent Application 20110281333 - Methane Production from Single-Cell Organisms; 2011; Abstract: The present invention relates to a method for enhancing the growth of single-cell organisms, such as methanogens. The growth of the single cell organisms includes consuming carbon dioxide to produce methane;
not only can CO2-free environmental energy be harness to drive CO2-recycling processes, but, biological mediators can be employed to facilitate, and reduce the energy requirements, of the needed reactions.)
Surely, there are already different possibilities to overcome the low reactivity of CO2, for example using high-energy reaction partners such as hydrogen, unsaturated compounds or strained cyclic molecules. However, when evaluating the overall energy balance and efficiency of the process, the energy used to generate these high-energy materials has to be taken into account, which is especially relevant regarding hydrogen. For a long time there were only very few reactions using CO2 that were efficient enough to be used in practice and the chemical utilization of carbon dioxide became known as the "dream reaction."
(Note that there are a number of catalyzed reaction pathways that enable the efficient reaction of Hydrogen with Carbon Dioxide to form hydrocarbons, the 1912 Nobel-winning Sabatier reaction among them. The drawback to them is the energy needed, as indicated above, to generate the Hydrogen. But, as seen, for just one example, in:
NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,045,315 - Solar Photolysis of Water; 1977; NASA; Abstract: Hydrogen is produced by the solar photolysis of water ... . A method of photolyzing water comprising the steps of: applying solar radiation to a first vessel containing an aqueous solution of a water soluble photo-oxidizable reagent (which) is a material which absorbs strongly in the solar range at ground level and is capable of photolyzing water to produce hydrogen";
with many more examples to follow, there are a number of ways, using environmental energy, and in some cases biological mediation, to efficiently generate Hydrogen.)
A core technology for the successful and economically interesting use of CO2 as a chemical feedstock is catalysis, one of the most sophisticated and complex research areas of modern chemistry. Catalysis is used in the production of more than 85% of all products of the chemical industry, and the catalyst by its nature strongly determines the outcome of the reaction and the final product formation.
(As above, non-biological, or inorganic, catalysis is another way to "leverage" the energy needed to "activate" the relatively inert Carbon Dioxide molecule, and to convert it into something more useful. An example can be seen in our report of:
Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development; concerning: "United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes; 1987; Assignee: The Standard Oil Company; Abstract: A process for the electrocatalytic reduction of carbon dioxide comprises immersing a transition metal complex with square planar geometry into an aqueous or nonaqueous solution which has been acidified to a (specified) hydrogen ion concentration ... , adding the carbon dioxide, applying an electrical potential of from about -0.8 volts to about -1.5 volts ... , and reducing the carbon dioxide to carbon monoxide".)
In order to find the right catalyst, Bayer initiated the project "Dream Reactions" in 2009 ... .
Here, the company and numerous well-known academic partners have been investigating the preconditions of using CO2 as building block for polyurethanes - a class of polymers widely used in every-day life, e.g. in mattresses, car seats, and as insulation materials. Polyurethanes are the reaction product of two components, isocyanates and polyols. The chemical nature of polyols gives them considerable potential for incorporating CO2. Consequently the possibilities of using it as building block for a new kind of polyols, so called polyether-polycarbonate polyols, have been investigated within the "Dream Reactions" project. A broad catalyst screening helped to identify promising candidates, which were then optimized in terms of activity and selectivity towards the desired product.
Finally, Bayer researchers succeeded in finding the one suitable catalyst for this special reaction - a scientific breakthrough after decades of fruitless research. Consequently, Bayer thought about going one step further: Within the energy industry, strategies for capturing CO2 from flue gases out of coal-fired power plants are discussed, yielding relatively pure CO2 in vast quantities. Why not combine the chemical industry with the energy sector and turn the "Dream Reaction" into a "Dream Production"?
Thus, another consortium was established, consisting of Bayer, German energy provider RWE Power and researchers from RWTH Aachen University. The project "Dream Production" is again partly funded by the German Federal Ministry of Education and Research within their strategy to enhance the utilization of CO2 as chemical building block. The consortium depictures the total value chain of CO2 utilization in a very unique way - from source to final product.
The overall goal is to make the discoveries from "Dream Reaction" become reality, i.e. to design and develop a technical process able to produce CO2-based polyether polycarbonate polyols on a larger scale. As a first major step, a pilot facility for the chemical treatment of carbon dioxide from the energy industry was opened at the Bayer Chempark Leverkusen in February 2011. Since then, the CO2 delivered from RWE Power is converted into the already mentioned polyether-polycarbonate polyols. These are then subsequently transformed into polyurethane samples tested for their material properties and competitiveness. The first results are encouraging. Though having a higher viscosity, the new polyols show similar properties as products already on the market and can be processed in conventional plants as well.
In parallel, the eco-efficiency of the new process is being compared with existing alternatives. Initial research, conducted by an independent team of scientists at RWTH Aachen University, seems to underpin the hypothesis that in the end real CO2 savings are reached. But the examination is very complex and will still last for a while. If progress continues, "Dream Production" will start bringing CO2-based products to market at 2015 earliest. The first application could be soft foam matresses.
In summary, even though the field of research is hardly new, the use of CO2 as a raw material is one of the most interesting and visionary technologies for the future. Since fossil resources are finite, using CO2 as a chemical feedstock is a promising approach to global carbon management, helping to pave the way to alternative sources of raw materials.
And the next time when people are asked to think about coal-fired power plants, the picture that comes into their minds might be just a bit different than before."
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Maybe we could start to get a "picture" of "coal-fired power plants" as being raw material factories; for, that, indeed, is what the electricity they primarily produce can in one sense be seen as. For instance, to make toast, we just mix bread and electricity in a conversion reactor called a "toaster", don't we?
And, the Carbon Dioxide can be seen as a raw material, as well.
We remind you, that, as in: "Polyurethanes are the reaction product of two components, isocyanates and polyols. The chemical nature of polyols gives them considerable potential for incorporating CO2", even though the CO2-based "polyols" are the focus of our subject herein, "isocyanates" are required to react with those CO2-based "polyols" to form "Polyurethanes".
And, as we discussed in:
Carbon Dioxide Recycled in the Manufacture of Plastics | Research & Development; concerning: "United States Patent 4,564,513 - Process for the Production of Carbon Monoxide; 1986; Assignee: Bayer Aktiengesellschaft (AG), Germany; Abstract: Carbon monoxide is produced in an improved process in a carbon-filled, water-cooled generator in the configuration of a truncated cone in the longitudinal section, by the gasification of said carbon with a mixed gas of oxygen and carbon dioxide"; and: "United States Patent Application 0040141901 - Process for the Desulfurization of CO Gas; 2004; Bayer Polymers, LLC, Pittsburgh, PA; Abstract: The present invention relates to a process for the preparation of carbon monoxide gas (CO gas) that is free of sulfur compounds to the greatest possible extent, to a process for the desulfurization of a CO gas containing sulfur, and to the use of that gas in chemical syntheses, for example for the synthesis of phosgene from carbon monoxide and chlorine";
Bayer knows how to react Carbon Dioxide with hot Coal to make Carbon Monoxide, which can then be reacted with Chlorine to make Phosgene, which is, we assert for you here, and as we will in future reports more fully document, the primary raw material for the making of the "isocyanates", as stipulated by Bayer above, for reaction with the CO2-based "polyols" to make "polyurethanes".
The Carbon Dioxide-recycling potential of this plastics-making concept is, thus, very roughly, doubled.
Should anyone be motivated enough to examine all of the Bayer documents available via the links in this dispatch, you'll note that one Bayer scientist explains that the CO2-recycling potentials of converting power plant Carbon Dioxide into "polyols" is only a relatively small piece of the puzzle, and, under the corporate sword of political correctness no doubt, genuflects in the ridiculous direction of geologic sequestration.
The worldwide market for polyurethanes, though, is huge; and, if we can make nearly all of the component raw materials for polyurethanes, as seen above, out of, primarily, Carbon Dioxide, the consumption of CO2 would still be very significant. And, that ignores other potentials, since other plastics can be made from polyol and isocyanate-type raw chemical materials. And, as seen in:
Conoco Converts CO2 to Methanol and Dimethyl Ether | Research & Development; concerning: "United States Patent 6,664,207 - Catalyst for Converting Carbon Dioxide to Oxygenates; 2003; Assignee: ConocoPhillips Company; Abstract: A catalyst and process for converting carbon dioxide into ... methanol and dimethyl ether";
we can convert Carbon Dioxide into Methanol, as well, which, as seen in:
SCC – Southern Chemical Corporation » Methanol; "Methanol can be found in a wide array of products used in our homes, cars and businesses (via manufacture of) resins ... used in engineered wood products like particleboard made from waste wood, and in products like seat cushions and Spandex fibers. Methanol-based acetic acid is used in making PET plastic, used to package beverages and household products and polyester fiber in clothing and carpets",
can also be used in the further synthesis of plastics and polymers in addition to the polyurethane made, as herein, by Bayer, from Carbon Dioxide.
All in all, we would think the "hidden value" of Carbon Dioxide is far too big to be "hidden" much longer.
