As we've documented and made reference to many times, as, just for two examples, in our reports of:
West Virginia Coal Association | US EPA Recommends Coal Liquefaction as a Clean Alternative | Research & Development; concerning: "Clean Alternative Fuels: Fischer-Tropsch; United States Environmental Protection Agency; EPA420-F-00-036; March 2002; A Success Story (!) For the past 50 years, Fischer-Tropsch fuels have powered all of South Africa’s vehicles, from buses to trucks to taxicabs. The fuel is primarily supplied by Sasol, a world leader in Fischer-Tropsch technologies. Sasol’s South African facility produces more than 150,000 barrels of high quality fuel from domestic low-grade coal daily.
West Virginia Coal Association | US EPA 1974 Coal to $15 per Barrel Gasoline | Research & Development; concerning: "A SASOL Type Process for Gasoline, Methanol, Synthetic Natural Gas and Low-Btu Gas from Coal;
EPA-650/2-74-072; Contract Number 68-02-1308; Prepared for: U.S. Environmental Protection Agency; 1974; Abstract: This report gives results of a study to assess costs and feasibility of manufacturing gasoline, methanol, Substitute Natural Gas and low-Btu gas from Coal, using the SASOL-type process. This process is based on a SASOL plant which has been operated commercially for more than 20 years for the manufacture of gasoline, fertilizers and other chemicals from Coal. SASOL's continued study of processes in their complex has doubtless given much fundamental information that would be a real asset to a designer tailoring a coal-to-gasoline facility twenty or more years after the original design was committed. It should be remembered that the products of the synthesis are remarkably free of many troublesome contaminants, e.g., metals, sulfur. (From Document page 63, File Page 71:) Gasoline Cost = $15.11/Barrel";some pretty impeccable sources have confirmed over multiple decades, with none of that confirmation being made available to the US public, most especially the US Coal Country public, at large, that the nation of South Africa has been profitably and cleanly converting Coal into perfectly-acceptable, even cleaner and perhaps cheaper, gasoline, diesel fuel and other hydrocarbons for well more than half a century.
As noted by the EPA, Sasol, aka South Africa Synthetic Oil Limited, although other translations of the name are also offered, makes their "high quality fuel from ... low grade coal" via "Fischer-Tropsch technologies", which, as explained by:
Fischer–Tropsch process - Wikipedia, the free encyclopedia; "The Fischer–Tropsch process is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogeninto liquid hydrocarbons. It was first developed by Franz Fischer and Hans Tropsch at the "Kaiser-Wilhelm-Institut für Kohlenforschung" in Mülheim an der Ruhr, Germany in 1925. The process, a key component of gas to liquids technology, produces a synthetic lubrication oiland synthetic fuel, typically from coal ... . The Fischer–Tropsch process has received intermittent attention as a source of low-sulfur diesel fuel and to address the supply or cost of petroleum-derived hydrocarbons. The largest scale implementation of Fischer–Tropsch technology are in a series of plants operated by Sasol in South Africa, a country with large coal reserves, but little oil. The first commercial plant opened in 1952, 40 miles south of Johannesburg";
require the initial gasification of Coal, to form a synthesis gas, or "syngas", blend of Carbon Monoxide and Hydrogen. And, as seen most recently in our report of:
West Virginia Coal Association | Germany Improves Coal Conversion To Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 8,562,698 - Device for Production of Synthesis Gas with a Gasification Reactor with a Subsequent Quenching Space; October 22, 2013; Assignee: ThyssenKrupp Uhde, GmbH, Germany; Abstract: The invention relates to a device for producing a crude gas containing CO or H2 by gasification of an ash-containing fuel. An apparatus for production of raw gas that contains CO and H2, by means of gasification of fuel that contains ash, with gas that contains oxygen";
the technology for generating such synthesis gas blends of Carbon Monoxide and Hydrogen from Coal continues to be improved, well more than half a century after it was first used to convert Coal indirectly into stuff like Gasoline and Diesel fuel on an industrial, commercial scale in South Africa.
And, herein we learn, that, not only can Coal be converted by South Africa, via Fischer-Tropsch technology, into Gasoline and Diesel, and, as per the US EPA in their report: "EPA-650/2-74-072;Contract Number 68-02-1308; Prepared for: U.S. Environmental Protection Agency; 1974" into "Substitute Natural Gas", it can also be converted into virtually anything we now rely on petroleum feedstock for our supply of, including the raw materials for synthesizing various plastics.
As seen in excerpts from the initial link in this dispatch, with an additional link and excerpt following:
"United States Patent 8,513,463 - Process for the Production of Nitrogen or Phosphorous Containing Compounds from Synthesis Gas
Date: August 20, 2013
Inventor: Michael Claeys, et. al., South Africa
Assignee: The University of Capetown, South Africa, and Carl Von Ossietzky Universitat Oldenburg, Germany
(As we've noted in other of our reports, so important is the business of converting Coal into hydrocarbon fuels and chemicals to the economy of South Africa, that other companies, as well as key institutions of higher learning, there are actively involved in supporting, promoting and furthering the industry. That a German institution of higher learning would be involved as well is unsurprising, since the key technologies for converting Coal into liquid and gaseous hydrocarbons originated in Germany early in the last century.)
Abstract: A process is described for the production of one or more of linear nitriles, amides and formamides which includes reacting a nitrogen containing compound, such as ammonia or NOx, and a synthesis gas over a catalyst at a temperature of between 160 and 400 C and a pressure of between 1 bar and 50 bar. A further process for the production of one or more of linear phosphorous containing compounds is also described, which includes reacting a phosphorous containing compound, such as a phosphine, and a synthesis gas over a catalyst at a temperature of between 160 and 400 C and a pressure of between 1 bar and 50 bar. A supported cobalt, iron, ruthenium or rhodium catalyst or an unsupported (bulk) promoted iron catalyst, modified with a promoter is used. The synthesis gas is a mixture of hydrogen and carbon monoxide, in a ratio from 0.5:1 to 5:1; or a mixture of hydrogen and carbon dioxide; or a mixture of water and carbon monoxide. The suppression of the formation of oxygenates in the process is a feature of the invention and oxygenates may even be included in the feed to become converted to corresponding nitrogen containing compounds in the process.
(First, the "oxygenates" which are undesirable to be produced herein, but which can be included, recycled back into, the feed, would include stuff like Methanol, a fuel alcohol, which would otherwise be some pretty nifty stuff to be making from Coal syngas. Second, though not well-explained, stuff like "ammonia or NOx", nitrogen oxides, would already be present to a certain extent in the syngas, if plain air were used for the Coal gasification. Third, the "nitriles" and "amides" are valuable in the synthesis of various sorts of commercial polymers, plastics; while the "foramides" are, as well, valuable industrial raw materials. See:
"Nitrile - Wikipedia, the free encyclopedia; Amide - Wikipedia, the free encyclopedia; and:Formamide - Wikipedia, the free encyclopedia.)
Claims: A process for the production of at least one nitrogen or phosphorus containing compound selected from linear nitriles, amides, formamides and linear phosphorous containing compounds from synthesis gas during the hydrogenation of carbon monoxide and or carbon dioxide components in a synthesis gas in a feed to a reactor in which a catalyst acts on the feed at a temperature of between 160 C and 400 C and under a pressure of between 1 bar and 50 bar, the process being characterized in that at least one nitrogen and phosphorous containing compound is fed to the reactor together with the synthesis gas and in that the catalyst is heterogeneous and the process conditions are selected to favour the production of said at least one nitrogen or phosphorus containing compound selected from linear nitriles, amides, formamides and linear phosphorous containing compounds.
A process .. in which the formation of oxygenates during the process is suppressed (and) in which one or more oxygenates is co-fed to the reactor to become converted to one or more corresponding nitrogen containing compounds.
A process ... in which the catalyst is unsupported promoted iron (and) is modified with one or more promoters selected from an alkali promoter, a reduction promoter and a structural promoter.
A process ... in which the nitrogen containing compound includes ammonia and NOx (and) in which the synthesis gas is a mixture of hydrogen and carbon monoxide (and) includes carbon dioxide.
(Depending upon how the syngas is generated, "ammonia and NOx" from an external source might or might not have to be added to the syngas.)
A process ... in which the synthesis gas includes water and carbon monoxide.
A process ... in which one or more of linear phosphorous containing compounds is produced by reacting a phosphorous containing compound and a synthesis gas over the catalyst (and) in which the phosphorous containing compounds include phosphines.
(As can be inferred from information in:
Phosphine - Wikipedia, the free encyclopedia; the "phosphine", which is toxic, would have to be added to the syngas from an external source.)
A process ... in which the oxygenates include alcohols ... (and) in which the hydrogenation reaction occurs as a Fischer-Tropsch reaction.
Fischer-Tropsch carbon monoxide hydrogenation is a catalysed process in which a carbon monoxide and hydrogen mixture, typically referred to a "synthesis gas" or "syngas", is converted into liquid hydrocarbons, predominantly linear hydrocarbons (olefins and paraffins) of different chain length. Small amounts of oxygenates, mainly alcohols, aldehydes and acids can also be formed. The products can be used to produce transportation fuels such as diesel and petrol as well as waxes. Alternately, or in addition, valuable chemicals such as olefins and oxygenates can be extracted from the product.
The synthesis gas can include carbon dioxide instead of carbon monoxide and water instead of hydrogen, and may alternatively include combinations of these reactants.
Literature from the 1960's and 1970's suggests that linear primary amines may be formed upon co-feeding of ammonia and other nitrogen-containing compounds to the synthesis gas during Fischer-Tropsch synthesis or other reactions involving synthesis gas. This may be a result of using iron based catalysts prevalent at the time as iron is known to catalyse ammonia production.
More recently, cobalt based catalysts have become an alternative to iron based catalysts as the most widely used in Fischer-Tropsch reactions and studies have found that nitrogen and nitrogen containing products act as a poison to these catalysts. Thus, whilst it is highly desirable to produce linear nitriles, amides and formamides from a synthesis gas feed, the prior art indicates that this is not viable as only amines are produced and as nitrogen based compounds poison cobalt based catalysts.
Summary: In accordance with this invention there is provided a process for the production of at least one nitrogen or phosphorus containing compound selected from linear nitriles, amides, formamides and linear phosphorous containing compounds from synthesis gas during the hydrogenation of carbon monoxide and or carbon dioxide in a synthesis gas in a feed to a reactor in which a catalyst acts on the feed ... , the process being characterized in that at least one nitrogen and phosphorous containing compound is fed to the reactor together with the synthesis gas and in that the catalyst and process conditions are selected to favor the production of said at least one nitrogen or phosphorus containing compound selected from linear nitriles, amides, formamides and linear phosphorous containing compounds.
Further features of the process provide for the catalyst to be selected for the catalyst to be selected from cobalt, iron, ruthenium and rhodium or mixtures thereof, for the catalysts to be modified with one or more promoters, but preferably unsupported promoted iron; for the iron catalyst preferably to be modified with one or more promoters including an alkali promoter such as potassium and a reduction promoter such as copper and a structural promoter such as alumina or silica; for the nitrogen containing compound to include ammonia and NO.sub.x; and for the reactor to be selected from a slurry phase reactor, a fixed bed reactor and a fluidised bed reactor.
According to one aspect of the invention there is provided for the synthesis gas to be a mixture of hydrogen and carbon monoxide; and for the ratio of hydrogen to carbon monoxide to be from 0.5:1 to 5:1.
According to a second aspect of the invention there is provided for the synthesis gas to be a mixture of hydrogen and carbon dioxide.
According to a third aspect of the invention there is provided for the synthesis gas to be a mixture of water and carbon monoxide.
According to a fourth aspect of the invention there is provided for the synthesis gas to be a mixture of all of hydrogen, water, carbon monoxide and carbon dioxide.
In one variation of the invention a process for the production of one or more of linear phosphorous containing compounds includes reacting a phosphorous containing compound and a synthesis gas over the catalyst.
A further feature of this variation of the invention provides for the phosphorous containing compounds to include phosphines.
The invention also provides a process for the suppression of oxygenates formation during the hydrogenation of one of carbon monoxide or carbon dioxide in a synthesis gas which includes co-feeding a compound containing either or both of nitrogen and phosphorous with the synthesis gas to the reactor.
The hydrogenation reaction may occur as a Fischer-Tropsch reaction."
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Basically, the building blocks of certain valuable polymers can be synthesized from synthesis gas derived from Coal, or, from a gas blend, variously, of Carbon Dioxide, Hydrogen, Carbon Monoxide and Water. That said, the same team of scientists concurrently explained how simpler, more pure hydrocarbons useful as plastics and polymers, or in the synthesis of plastics and polymers, can be derived from the same blend of gases by varying the catalyst employed; as seen in:
"United States Patent: 8558047 - Process for the Production of Hydrocarbons Including Olefins from Synthesis Gas
Date: October 15, 2013
Inventors: Michael C. M. Claeys, et. al., South Africa
Assignee: University of Capetown, South Africa
Abstract: A process is provided for the production of hydrocarbons from synthesis gas wherein the synthesis gas is fed to a reactor in which a catalyst acts on the feed at a temperature of between 160 and 400 C and a pressure of between 1 bar and 5 bar. The feed includes a compound containing one or both nitrogen and phosphorus added to the reactor with the synthesis gas. The compound containing nitrogen typically constitutes at least 1 vol % and preferably of the order of 4 to 20 vol % or more of the feed. The carbonaceous gas may be carbon monoxide with a ratio of hydrogen to carbon monoxide in the synthesis gas of from 0.5:1 to 5:1. The catalyst is preferably a supported cobalt catalyst and may be modified with a promoter. The process produces an enhanced proportion of olefins, in the hydrocarbons produced.
Claims: A process for the production of hydrocarbons from synthesis gas, the process comprising: Feeding to a reactor: (a) a synthesis gas comprising at least one carbonaceous gas component that is carbon monoxide or carbon dioxide; and (b) at least one compound comprising nitrogen wherein the nitrogen compound constitutes at least 4 vol % of the feed wherein the reactor comprises a catalyst that acts on the synthesis gas at a temperature of between 160 and 400 C and under a pressure of between 1 bar and 50 bar and the process conditions that are selected to favor the production of olefins over other hydrocarbons.
The process ... wherein the nitrogen compound constitutes at least 20 vol % of the feed (and) wherein the at least one compound further comprises a phosphorous compound and wherein the phosphorous compound constitutes at least 0.01 vol % of the feed (and) wherein the catalyst is selected from cobalt, iron, ruthenium and mixtures thereof (and) wherein the catalyst is a cobalt catalyst supported on a suitable carrier material including any one or more of alumina, silica, titania and carbon.
The process ... wherein the nitrogen compound is ammonia.
The process ... wherein the carbonaceous gas component is predominantly carbon monoxide.
(Since "the carbonaceous gas" used as feed can be "predominantly carbon monoxide", we remind you of an alternative gasification process which might be utilized to good effect herein, as explained in our report of:
West Virginia Coal Association | Bayer Improves Coal + CO2 = Carbon Monoxide | Research & Development; concerning: "United States Patent 7,473,286 - Carbon Monoxide Generator; 2009; Assignee: Bayer Material Science, AG, Germany; 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 ... . 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). 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) ... . 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";wherein high-purity Carbon Monoxide can be synthesized by reacting hot Coal with Carbon Dioxide.)
The process ... wherein the synthesis gas comprises hydrogen and carbon monoxide and the ratio of hydrogen to carbon monoxide in the synthesis gas is from 0.5:1 to 5:1.The process ... wherein the carbonaceous gas component comprises carbon dioxide and wherein the synthesis gas is predominantly a mixture of hydrogen and carbon monoxide and/or carbon dioxide (or) wherein the synthesis gas comprises hydrogen, water, carbon monoxide and carbon dioxide.
The process ... wherein the process conditions are selected to favor the production of olefins over paraffins.
(Olefins | Petrochemicals Production | Refinery Petrochemicals | Olefins Production | Olefins Process | KBR: A Global Engineeri; "Olefins are in a class of hydrocarbons with a ... chemical formula of C(n)H(2n). The two most important olefins are ethylene and propylene, as they form the backbone of the petrochemicals market. The highly reactive double bond makes the olefin molecule ideal for conversion to many useful end products. The majority of olefins capacity is consumed in the production of polymers used for plastics (i.e. polyethylene and polypropylene). Ethylene dichloride, ethylene oxide, propylene oxide, oxo alcohol, polystyrene, and acrylonitrile are other important olefins-based petrochemicals. Worldwide olefins demand is primarily driven by economic growth and the associated increased demand for consumer goods.")
Background and Field: This invention relates to a process for the production of hydrocarbons from synthesis gas and, more particularly, to a process in which the production of olefins, especially linear olefins, during the relevant reactions of carbon oxides is enhanced.
Fischer-Tropsch carbon monoxide hydrogenation is a catalysed process in which a carbon monoxide and hydrogen mixture, typically referred to a "synthesis gas" or "syngas", is converted into liquid hydrocarbons, predominantly linear hydrocarbons (olefins and paraffins) of different chain length. Small amounts of oxygenates, mainly alcohols and aldehydes, can also be formed. The products can be used to produce transportation fuels such as diesel and petrol. Alternately, or in addition, valuable chemicals such as olefins and oxygenates can be extracted from the product.
The synthesis gas can include carbon dioxide as well as carbon monoxide or water as well as hydrogen, and may also include combinations of all four of these reactants.
There is a considerable difference in the value of paraffins and olefins with mixtures predominating in paraffins being of relatively low value and primarily usable for the production of transportation fuels and waxes, whilst olefins themselves, are of substantially greater value and are usable for numerous other purposes.
Summary: In accordance with this invention there is provided a process for the production of hydrocarbons from synthesis gas during the hydrogenation of a carbonaceous gas component in a synthesis gas in a feed to a reactor in which a catalyst acts on the feed at a temperature of between 160 and 400 C and under a pressure of between 1 bar and 50 bar, the process being characterised in that at least one compound containing one or both of nitrogen and phosphorous is fed to the reactor together with the synthesis gas and in that the catalyst and process conditions are selected to favor the production of olefins.
According to (one) aspect of the invention there is provided for the synthesis gas to be a mixture of water and carbon monoxide (and, according to (another) aspect of the invention there is provided for the synthesis gas to be a mixture of ... hydrogen, water, carbon monoxide and carbon dioxide. "
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In sum, starting with Coal, we can manufacture, through the generation of synthesis gas, a broad range of commodity polymers; that is, plastics, which are currently made in large part from petroleum-based raw materials.
However, we are compelled to remind you, that, should we wish to conserve our precious Coal for it's essential use in the generation of truly abundant, truly affordable and truly reliable electric power, then, as seen for only one example in our report of:
West Virginia Coal Association | More USDOE CO2 "Syntrolysis" | Research & Development; concerning: "Co-Electrolysis of Steam and Carbon Dioxide for Production of Syngas; Fifth International Fuel Cell Science, Engineering and Technology Conference; July, 2007; J.E. O'Brien, C.M. Stoots, et. al.; Idaho National Laboratory, USDOE; and Ceramatec, Inc., Utah; Abstract: An experimental study has been completed to assess the performance of single-oxide electrolysis cells ... simultaneously electrolyzing steam and carbon dioxide for the direct production of syngas. Introduction: A research project is underway at the Idaho National Laboratory (INL) to investigate the feasibility of producing syngas by simultaneous electrolytic reduction of steam and carbon dioxide ... . Syngas, a mixture of hydrogen and carbon monoxide, can be used for the production of synthetic liquid fuels via Fischer-Tropsch processes. Conclusion: Based on the results obtained to date, coelectrolysis of steam and carbon dioxide for direct production of syngas appears to be a promising technology that could provide a possible path to reduced greenhouse gas emissions and increased energy independence, without the infrastructure shift that would be required for a hydrogen-based transportation system";
as confirmed by our own United States Department of Energy, we can make any "synthesis gas ... mixture of ... hydrogen, water, carbon monoxide and carbon dioxide" we might want or need by starting with only Water and Carbon Dioxide.