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We have previously cited the carbon conversion work of Richard Noceti, and colleagues, at the USDOE Pittsburgh (PA) Technology Center.
Although we would prefer to avoid redundancy, we must again reference Noceti, and colleague Charles Taylor, as they herein affirm that Methane, once it has been generated by Coal gasification or Sabatier-type Carbon Dioxide recycling and conversion, can itself be converted into gasoline.
We submit their report of this work as further confirmation that technologies, multiple technologies, exist, which would, if reduced to practice, enable the United States to achieve some level of domestic liquid fuel self sufficiency, an improving environment through greenhouse gas recycling, and, through increased reliance on domestic resources, a dramatically improved economy.
However, we append what we think to be important comment following the excerpt:
"CONVERSION OF METHANE TO GASOLINE-RANGE HYDROCARBONS
Charles E. Taylor and Richard P. Noceti
U.S. Department of Energy
Pittsburgh Energy Technology Center
P.O. Box 10940
Pittsburgh, PA 15236
Existing processes have been assembled in a novel combination capable of producing higher hydrocarbons from methane with high yield and selectivity. Methane, oxygen, and hydrogen chloride react over an oxyhydrochlorination (OHC) catalyst in the first stage to produce predominantly chloromethane and water. In the second stage, the chloromethane is catalytically converted to higher hydrocarbons, namely, paraffins, cycloparaffins, olefins, and aromatics, by an alumino-silicate zeolite. In the process described, the final hydro- carbon mixture is largely in the gasoline (C4-C10) boiling range.
Current technology for the conversion of methane to more useful compounds includes steam reforming reactions; halogenation; oxychlorination; oxidation, including oxidative coupling and metal oxide reactions; reaction with superacids; and various other methods. At present, these conversion schemes are unattractive because they are marked by low overall carbon conversions or poor selectivities.
In 1975, Mobil Oil Corporation patented a process.for the conversion of methanol to higher ,hydrocarbons by reaction over a zeolite catalyst, such as ZSM-5. Although later Mobil patents claimed that ZSM-5 wouId convert any monofunctionalized methane to higher hydrocarbons, methanol was the feedstock of interest.
In work done by Allied Chemical Corporation, Pieters, et al., reported the selective functionalization of methane by reaction with oxygen and hydrogen chloride over a supported copper chloride catalyst to give tetrachloromethane as the major product. The advantages of the Allied process are significant.
The work described below demonstrates that an effective method for selective functionalization in combination with oligomerization over a zeolite catalyst provides a facile route for conversion of methane to higher hydrocarbons.
The zeolite catalyst was regenerated by exposure to oxygen at temperatures between 350° and 550°C until the presence of carbon dioxide in the effluent stream was no longer detected by the mass spectrometer.
Removal of carbon restored the catalyst to its initial activity even after 14 cycles.
RESULTS
Conversion of methane to chloromethane
The conversion of methane to chloromethane has been observed under various reaction conditions. The data show a material balance around 100% and display several trends. ... methane conversion and polychlorination both increase as residence time and temperature increase.
Production of carbon dioxide and formic acid, undesirable by-products, also varied with residence time and temperature. As either the residence time or temperature increased, the amount of carbon dioxide increased while the amount of formic acid decreased. Carbon monoxide was not detected in the product stream.
Conversion of chloromethane to gasoline
Conversion of chloromethane over ZSM-5 to gasoline-range hydrocarbons has been observed to occur under conditions similar to those for the conversion of methanol. Two forms of the oligomerization catalyst were used in this study. One was a sample of iron-promoted ZSM-5 synthesized in our laboratory; the other was a sample of H-ZSM-5 obtained from Mobil Oil Corporation. Both catalysts produced similar products under the same reaction conditions.
Conclusion
Methane has been converted to higher hydrocarbons boiling in the gasoline range by the two-stage process described."
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Although it is herein documented that Methane, as could be produced by Coal gasification or the Sabatier recycling of Carbon Dioxide, can be converted almost directly into higher, "gasoline-range hydrocarbons", there might be an even better use for it, a better way to convert it into those higher hydrocarbons.
Methane could, instead, be reacted with even more Carbon Dioxide in a "Tri-reforming" process, as described by Song and Grimes, et. al., at Penn State University, and as we have documented in our recent reports. If Methane produced by Sabatier CO2 recycling technology were employed in that process, even more Carbon Dioxide would thus be utilized and consumed.
One contrary note: "Formic acid" is referred to herein as an "undesirable by-product". Actually, formic acid does have practical applications, including use in fuel cells, which might have evolved since this report was issued. It does now have commercial value, and if it is produced in significant quantity, it could represent another income stream for this technology.
In any case, it is again demonstrated that multiple technologies exist which would, if reduced to commercial practice, enable all US citizens to enjoy the economic and international relations benefits of a domestic liquid fuel self-sufficiency based on Coal; on products, like Methane, which can be made from Coal; and, on the byproducts, such as Carbon Dioxide, of Coal use.
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As we have thoroughly documented in reports from Penn State University, and others, Carbon Dioxide can be recycled, through the process of "Tri-reforming", wherein it is combined with Methane in a reaction sequence that yields complex hydrocarbons, including some which can be used as, or refined into, liquid fuels.
We have also cited reports, including one most recently from the Pittsburgh, PA, office of the USDOE, demonstrating that Methane, alone, can be converted both into the liquid fuel and gasoline synthesis raw material, Methanol, and, even more directly, into gasoline-range hydrocarbons.
We have thoroughly documented that Carbon Dioxide can be used as a raw material from which Methane can be synthesized, especially via the Nobel-winning Sabatier process, as is now being further developed by NASA; and, other technologies, that we've referred you to, patented by corporate proxies of our US Department of Defense.
We have also reported, via citation of multiple, credible sources, some dating back to the 1950's, that Methane can, as well, be manufactured by processes of Coal gasification.
Herein, in a more recent report, only a quarter-century old, the fact that Coal can be converted into Methane is affirmed by no less a hydrocarbon fuel authority than Exxon.
As per the excerpt:
"Title: Dynamic simulation of Exxon's Catalytic Coal-Gasification process
Authors: Franklin, H.D.; Parnas, R.S.; Kahn, C.; Gaitonde, N.Y.
Affiliation: Exxon Research and Engineering Co., Texas
Publication: Presented at the Annual Meeting of Heat Transfer and Energy Conversion, Los Angeles, 14 Nov. 1982
Abstract: A dynamic simulation of the Catalytic Coal Gasification (CCG) process was done to determine whether the process interactions presented any controllability problems as well as to help design a control scheme for the process. While there were previous dynamic simulation of both fixed and fluidized bed coal gasifiers, these simulations were all performed for noncatalytic gasification processes, and thus would not show the process dynamics implications resulting from the unique features of the CCG process. Unique features of closed control loop responses are given. The Exxon Catalytic Coal Gasification process is a novel method for producing methane directly from coal. Its key features from a process dynamics standpoint are use of a catalyst which causes both the highly endothermic gasification and exothermic methanation reactions to occur in the same reactor, separation of product gas in a highly heat-integrated cryogenic section, and recycle of product carbon monoxide and hydrogen back into the reactor."
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So, yes, in case you had any remaining doubts: If we want Methane for use in the recycling of Carbon Dioxide into valuable hydrocarbons, as can be accomplished via the "Tri-reforming Process" described by Penn State University; or, if we want Methane to convert directly into liquid fuels in a process such as that described by researchers Noceti, et. al., at the Pittsburgh DOE center, we have available, according to Exxon, a "method for producing methane directly from coal".
Why aren't we now employing that "method"?
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We have previously cited George Olah, of the University of Southern California's Loker Hydrocarbon Institute, on the subject of Carbon Dioxide recycling to valuable hydrocarbons.
Herein, it is documented that, very recently, Dr. Olah, and colleagues, have been awarded a United States Patent on technology to recycle Carbon Dioxide into the quite valuable hydrocarbons, which, in many previous reports, we have documented the utility of: Methanol and Dimethyl Ether.
The excerpt:
Title: Efficient and selective chemical recycling of carbon dioxide to methanol, dimethyl ether and derived products
Patent ID: US7608743
Issue Date: October 27, 2009
Abstract:
Patent ID: US7608743
Issue Date: October 27, 2009
Abstract:
An efficient and environmentally beneficial method of recycling and producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning powerplants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by chemical or electrochemical reduction secondary treatment to produce essentially methanol, dimethyl ether and derived products.
Inventors: George Olah and G.K. Surya Prakash
Assignee: University of Southern California"
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We won't go into further detail. The patent itself is full of details, and should be read carefully by anyone truly interested in how the Carbon Dioxide byproduct of our Coal-use industries is a precious commodity, a raw material that can be transformed, on a practical basis, into liquid fuels and plastics manufacturing raw materials.
This, we insist, puts the official lie to portrayals of Carbon Dioxide as a dangerous pollutant, a waste that we must be compelled by law to pay to have ineffectively sequestered, or be punished through Cap & Trade taxation for producing.
By the way: The "derived products", from Methanol and DME, which themselves result from CO2 recycling, would be such things, as we have documented, as diesel fuel, gasoline and plastics.
Carbon Dioxide, as now officially recognized by our United States Government, is a valuable raw material resource that can be recovered as a byproduct of our Coal-use industries.
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In a previous submission, we documented how researchers in Japan had developed a method, using catalysts employed by indirect Coal-to-liquid conversion technologies, to convert Carbon Dioxide into Ethanol, which can itself be further converted to, or used directly as an additive for, Gasoline.
Herein, it's reported by other Japanese scientists that Carbon Dioxide can also be converted, via Methanol, as we have documented from other credible sources to be feasible and practical, into Gasoline-range, and other, hydrocarbons.
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Subject: Stewart, CoalTL: Japan Recycles CO2 Directly to Ethanol
The promoters of environmental consciousness, and the peddlers of environmental "solutions", some of whose true motives, as we've documented, might be, like our environment, somewhat less than pristine, have long pushed, among other things like Sequestration, the concept of using Ethanol, derived at great expense and with high carbon emissions, all as we've documented, from our food supply, as a "clean" replacement, or additive, for our gasoline.
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