This past June, we provided you with more information concerning the Carbon Dioxide recycling and reuse technology, based on reactions between Carbon Dioxide and red-hot Coal, that has, or had, been under development by the German parent company of the Ohio Valley's Bayer Corporation, who are headquartered in Pittsburgh, PA, and who have significant manufacturing facilities in West Virginia.
That report is accessible via:
Carbon Dioxide Recycled in the Manufacture of Plastics | Research & Development; and, it included, among other things, information concerning:
"United States Patent 4,564,513 - Process for the Production of Carbon Monoxide; 1986; Bayer Aktiengesellschaft (AG), Germany; 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".
Herein, we present additional information, concerning advancements made by Bayer on that and related Carbon Dioxide recycling technology, along with some more documentation affirming the industrial utility of the CO2-based Carbon Monoxide produced by that technology, wherein Carbon Dioxide, recovered from whatever source, is reacted with hot Coal and a restricted amount of Oxygen .
We caution that Bayer's Disclosure is much more of a detailed description of the mechanics of the thing, than it is an exposition of the Carbon Dioxide chemistry involved; chemistry which their accomplished scientists likely tend to think of as an elementary, even obvious, reaction sequence that shouldn't require much explanation.
Too bad, that, in US Coal Country, it seemingly does.
Comments, and additional links, follow excerpts from the initial link herein to the fairly recent:
"United States Patent 7,473,286 - Carbon Monoxide Generator
Date: January, 2009
Inventor: Herbert Blaschke, et. al., Germany
Assignee: Bayer Material Science, AG, Germany
Abstract and Claims: A generator including a double-chamber lock comprising two tapered or vertical chambers lined with ceramics or plastics, as a charging device, at least one tubular shaft furnace comprising a water-cooled double jacket of steel, a double-walled, water-cooled inlet nozzle of copper for a gasification mixture, arranged centrally in the tubular shaft furnace above the base, a dry dust-removing device, and optionally a desulfurising device. The double-chamber lock has a mechanism which causes one of the chambers to open when the lower chamber of the double-chamber lock is flushed with inert gas after charging/opening operations, and the inlet nozzle constitutes the mixing member for the constituents of the gasification mixture, the inlet nozzle has a radius of curvature of the surface of the cylindrical portion of the nozzle which continuously becomes smaller to the outlet opening, and the direction of flow of the gases leaving the inlet nozzle is directed upwards.
The generator ... further comprising a desulfurizing device.
Background and Field: 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 ... .
The principle of a vertical shaft furnace for such thermal processes has been known for a long time (and) attempts have repeatedly been made in the past to improve the gasification of coal in various respects.
There has also been no lack of attempts to improve the difficult process of discharging residues, predominantly in the form of liquid slag, from the shaft furnace during the gasification of coal.
The major disadvantage of (cited prior art) processes is that the combustion residues do not occur in finely divided solid form which could be discharged with the flue dust, but must be discharged in the form of liquid slag, which is difficult to handle.
An object of the present invention was ,,, to provide a continuous process for the production of CO gas by the gasification of coal using the generator according to the invention, which process does not exhibit the disadvantages (of the) described (prior art).
A further object of the invention was to produce a CO gas having a purity of greater than 96%, preferably from 97 to 98%.
(Those ranges of purity for Carbon Monoxide made by reacting Carbon Dioxide with hot Coal are consistent with quite similar technology developed by others in Germany, as we reported in:
Germany 98% Pure Carbon Monoxide from Coal, CO2 and O2 | Research & Development; concerning: "Carbon Monoxide from Coke, Carbon Dioxide and Oxygen; Hydrocarbon Process(US); 1986; Lurgi GmbH, Frankfurt (Germany); The purpose of (this) process .. is to gasify coke using a mixture of CO2 and O2 as gasification agent ... . Depending on the quality of the feedstocks the produced gas shows a (Carbon Monoxide) concentration of 97 to 98.5% by volume. This CO level makes for an excellent feedstock for most syntheses.")
The present invention also provides a process for the production of carbon-monoxide-containing gas including reacting a carbon-containing combustion material in the above-described generator, where the carbon-containing combustion material has a ... carbon content of at least 85 weight %, an ash content of not more than 5 weight %, a content of water adhering to the surface of less than 10 % and an iron content of not more than 5000 ppm.
(As can be learned via:
DOE Coal Sample Bank & Database at the EMS Energy Institute; wherein we're told:
"Penn State is maintaining a suite of 56 coals and a corresponding computerized database of analyses for use by DOE contractors and grantees. The coals represent a wide spectrum of the major coalfields of the United States and were selected in order to achieve a useful distribution of important coals by rank, geologic province, maceral composition, sulfur content and forms, and ash yield and composition";
a number of local, WV and PA, Coals meet, or very nearly meet, Bayer's specifications.
For instance, "Sewell" Seam Coal from Greenbrier County, WV, has 4% ash and 89% carbon, well within the Bayer guidelines.
"Pittsburgh" Seam Coal from Washington County, PA, though, has 9% ash and 85% carbon, and is a shade high on the ash content.
Information on Iron contents is a little harder to come by; but, we bet that a scheme could be devised for blending various Appalachian Coals, perhaps in combination with a little naturally CO2-recycling charcoal, in such a way that the Bayer raw material specifications could easily be met.
And, such multi-Carbon source use, for CO2-recycling reactions, is, in fact, described in our recent report:
Chevron CO2 Converts Carbon-Recycling Wastes to Syngas | Research & Development; concerning: "United States Patent 3,850,588 - Production of Synthesis Gas Rich in Carbon Monoxide; 1974; Chevron Research Company; A carbon-monoxide-rich synthesis gas is produced by feeding a mixture of carbon dioxide and an organic material to a reaction zone (and, the invention) relates to the production of synthesis gas rich in carbon monoxide by the reaction of carbonaceous material with carbon dioxide. Synthesis gas rich in carbon monoxide is especially useful in the synthesis of methanol (and) as a feed for a Fischer-Tropsch synthesis for the production of hydrocarbons";
wherein it's seen that virtually any substance which can be labeled as a "organic material", which would include Coal, of course, and a lot of other things, can be reacted via these technologies with Carbon Dioxide and be made thereby to form either nearly-pure Carbon Monoxide, or, a hydrocarbon "Synthesis Gas Rich in Carbon Monoxide".
Thus, with Coal as the primary fuel and energy source, both reclaimed, gaseous Carbon Dioxide and already-recycled Carbon Dioxide in the form of virtually any botanically-sourced "organic material", such as Charcoal, can be utilized in these processes to form an "especially useful" product.)
In contrast to other processes of the prior art, the reaction in the combustion zone is controlled by injecting CO2 and O2 into the furnace together through the (described apparatus) ... so that the (O2) is diluted by the stream of CO2 gas. Adequate mixing of the gases is achieved by means of suitable mixing devices (as suggested).
In this manner, the two reactions that take place ..., C + O2 (and) CO2 + C ... are concentrated in a single controllable combustion zone and are not separate and distributed over several zones in the apparatus, as described in (prior art). This concentration of the reaction sequence in a single combustion zone makes the monitoring of process parameters considerably more simple and reliable. By varying the ratio of CO2 to O2 in the gas mixture that is fed in, according to the type of fuel and the properties of the fuel, the reaction temperature can be controlled (as well as) the degree of purity of the CO gas.
A sufficiently high oxygen supply is ... necessary in order to keep the furnace temperature sufficiently high by means of the exothermic oxidation reaction.
(As above, purified or concentrated Oxygen is required for this Bayer CO2-recycling process, and, as in:
USDOE Algae Make Hydrogen for Coal and CO2 Hydrogenation | Research & Development; concerning: "Photosynthetic Hydrogen and Oxygen Production by Green Algae; 1999; Oak Ridge National Laboratory; Abstract: Photosynthesis research at Oak Ridge National Laboratory is focused on hydrogen and oxygen production by green algae in the context of its potential as a renewable fuel and chemical feed stock";
it might be feasible to make some of the needed Oxygen by cultivating certain strains of Green Algae, which, when fed Carbon Dioxide, as from a Coal-fired power plant, produce, in alternating cycles, both Hydrogen, which could be combined with the Carbon Monoxide produced by the process of our subject, "United States Patent 7,473,286 - Carbon Monoxide Generator", to make a blend of Carbon Monoxide and Hydrogen, a synthesis gas, suitable for, as in the Fischer-Tropsch process, catalytic condensation into liquid hydrocarbon fuels; and, the Oxygen required to help drive the CO2-Coal reaction of "USP 7,473,286".)
(The) CO gas produced in the generator according to the invention ... contains dust, the so-called flue ash. This is solid, dust-like ash portions which are discharged from the furnace with the CO gas stream together with carbon that has not been burned, so that there is no build-up of ash in the furnace and accordingly no impairment of the operation of the furnace. The so-called run, that is to say the uninterrupted operating time of a furnace, in the process according to the invention may thus be several months and accordingly makes a decisive contribution to the utilization of the capacity of the installation and to the low outlay in terms of maintenance of such an installation.
The flue ash is a mixture of substances such as, for example, inorganic constituents of the mentioned fuels, which are present after the gasification predominantly in the form of the metal oxides (and) optionally metal halides, and on the other hand it is fine fuel particles which have formed in the combustion zone owing to the decomposition of the fuel during the gasification operation and escape from the combustion zone so rapidly, owing to the high gas speed in the furnace, that they participate in the reaction only incompletely and are drawn off with the gas stream.
This flue ash can contain up to 80 %, preferably up to 60 %, carbon and represents a safety risk in the further use of the CO gas because the functioning of downstream parts of the installation is impaired considerably by deposits of these particles therein. It is therefore important to separate such flue ash particles from the CO gas as quantitatively as possible, directly downstream of the tubular shaft furnace if possible, in order to avoid unnecessarily long paths for the dust-containing gas (and accordingly deposits). For this reason, the furnace is followed by a dry dust-removing device, upstream of which there is arranged a cyclone dust collector for separating coarser particles from the emergent CO gas stream and returning them to the furnace. This cyclone dust collector is located in the CO gas outlet pipe in the upper part of the furnace.
(Note that the "flue ash" is recycled to a certain extent, to ensure complete use of the available Carbon, some of which might otherwise escape as soot and be wasted. The remainder will consist in large part of "metal oxides", and we thought that we had previously documented the potentials for recovering metals from such "pre-refined" Coal ash. But, we can't at this time locate any earlier reports we might have made on that topic, and will make a point of providing you with information on those potentials in the near future.
But, once all the value, carbon or metal, has been extracted, the remaining, inert ash, like the very similar Coal-fired power plant fly ash, will still have potentials for use, as in, for one example:
Scientists Convert Coal Ash to Cement | Research & Development; concerning: "New Use for Coal Ash: Material Provides Strong and Lightweight Alternative to Concrete – without Cement; An assistant professor in Georgia Tech’s School of Civil and Environmental Engineering ... has developed a new structural material based on these leftovers from coal burning. Known as Cenocell (TM), the material offers attributes that include high strength and light weight – without the use of cement, an essential ingredient of conventional concrete.")
For energy reasons, the dust removal should take place at the outlet temperature of the CO gas from the furnace and the correspondingly high pressure, in order to avoid the unnecessary supply of further energy in a subsequent process step at high temperature. .
The dust-free CO gas still contains inorganic and organic sulfur compounds, which may be troublesome in further use, for example for the preparation of phosgene.
(Such "phosgene", again as seen in:
Carbon Dioxide Recycled in the Manufacture of Plastics | Research & Development; which contained separate report of: "US 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";
is made by reacting Carbon Monoxide with Chlorine gas, and is a quite valuable raw material for the manufacture of a number of very useful plastics, including, through intermediary raw materials, some polyurethanes, wherein the Carbon Dioxide, consumed through and via our subject process, of "United States Patent 7,473,286", would be forever, and productively, and profitably, "sequestered".
But, any residual Sulfur must be removed from the Carbon Monoxide before it can so utilized.)
The CO gas so produced may (thus) be passed directly into a subsequent desulfurisation device.
Volatile constituents in the fuel can likewise cause problems if they are relatively large amounts of hydrocarbons or water. Under the reaction conditions in the combustion zone, hydrocarbons form methane and hydrogen; hydrogen is also formed from water that passes into the combustion zone. Methane and hydrogen are tolerable as secondary products in the CO gas only within certain limits, because these products would be chlorinated when the CO gas is used to produce phosgene. The formation of HCl is to be avoided for reasons of corrosion, and the formation of carbon tetrachloride for reasons of toxicity.
Suitable fuels which meet the above-mentioned demands and which can be reacted successfully in terms of technology and economy to CO gas in the process described herein are, for example ... coal coke."
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Since "coal coke" is the preferred co-reactant for Carbon Dioxide in this CO2-recycling process, we'll close our excerpts there to voice the supposition, the hope, that we still know how to make a little "coal coke" in heart of US Coal Country, and, to remind you that, if we do, then coking a little Coal for utilization in Bayer's Carbon Dioxide conversion and recycling process can, as seen in:
WVU Hydrogenates Coal Tar | Research & Development; concerning the: "Hydrogenation of Naphthalene and Coal Tar Distillate; West Virginia University; 2009; The hydrogenation of naphthalene and coal-tar distillates has been carried out in a Trickle Bed Reactor ... (to form) the hydrogenated product, tetralin (which can be used to effect) the direct reaction between coal and hydrogen (and) the conversion of coal to refinable crude hydrocarbons, from which liquid fuels such as gasoline, diesel, kerosene, etc., can be produced", and:
Coke Oven Gas to Synfuel | Research & Development; concerning, in part: "Second Methanol Unit Based on Coke Oven Gas; The 120 000 t/a methanol project based on coke oven gas designed by the Second Design Institute of Chemical Industry (has) started production... . The capacity of this unit is 40 000 t/a higher than the first methanol unit based on coke oven gas in China complete in ... December 2004";
lead to the co-generation of some very intriguing by-products, i.e.,"coal-tar distillates" and "coke oven gas".
And, we are compelled to remind you, that, as affirmed by one example in:
Pittsburgh 1951 Carbon Monoxide + Water = Hydrocarbons | Research & Development; concerning: "United States Patent 2,579,663 - Process of Synthesizing Hydrocarbons; 1951; Gulf Research and Development Company, Pittsburgh; Abstract: This invention relates to a process for synthesizing hydrocarbons; more particularly the invention relates to a process for synthesizing normally liquid hydrocarbons from carbon monoxide and steam";
once we have the "96% ... to 98%" pure Carbon Monoxide, made so efficiently from Coal and Carbon Dioxide via our subject Bayer process of "United States Patent 7,473,286"; we can rather simply mix that Carbon Monoxide with plain old hot water, "steam", and thereby synthesize some "liquid hydrocarbons".
Or, perhaps more traditionally, we can mix that Carbon Monoxide with some of the Hydrogen, co-produced with the Oxygen, as we suggested above in our citation of "Photosynthetic Hydrogen and Oxygen Production by Green Algae; 1999; Oak Ridge National Laboratory"; which can be utilized in the process of "United States Patent 7,473,286" to help convert Coal and CO2 into Carbon Monoxide, and thereby form a blend of Carbon Monoxide and Hydrogen, a "syngas", which, as seen for just one example in:
British Petroleum Coal Syngas to Motor Fuels | Research & Development; concerning: "United States Patent Application 20090298958 - Fischer Tropsch Process; 2009; BP Exploration Operating Company Limited, Sudbury on Thames; The present invention relates to a process for converting synthesis gas to hydrocarbons ... particularly suitable for use as liquid motor fuels";
We can then catalytically condense, through a process first invented early in the prior century, and which has since undergone many improvements, into virtually any sort of petroleum-type product we now rely on increasingly unreliable, increasingly expensive and dangerous, foreign sources for the supply of.