As we've previously reported, both Auburn University, in Alabama, a member, with West Virginia University, of the Consortium for Fossil Fuel Science, and the Air Products and Chemicals Company, in Pennsylvania, have worked under various contracts with our United States Department of Energy in the development of Coal liquefaction technologies targeted on the conversion of Coal into petroleum substitute products.
Herein, we learn that they have actually collaborated, for the USDOE, on the development of such technologies, and together achieved significant improvements in the ways in which Coal, and Hydrogen donor solvents based on Coal tars, can be processed and reacted in order to improve the rates and productivity of processes that convert Coal into liquid hydrocarbons.
First, with additional links and excerpts inserted and appended, we present excerpts from the above link to:
"United States Patent 4,374,016 - Process for Hydrogenating Coal and Coal Solvents
Date: February, 1983
Inventors: Arthur Tarrer and Ketan Shridharani, Alabama
(Note: As can be learned via:
Tarrer is an Auburn University Professor of Chemical Engineering whose interests and expertise actually center now on bio-diesel production. Shridharani, too, at the time this patent was issued, was at Auburn University, though his current status is unknown.)
Assignee: Air Products and Chemicals Company, Pennsylvania
Government Interests: The government of the United States of America has rights in this invention pursuant to Contract No. DE-AC22-79ET14806 awarded by the U.S. Department of Energy.
Abstract: A novel process is described for the hydrogenation of coal by the hydrogenation of a solvent for the coal in which the hydrogenation of the coal solvent is conducted in the presence of a solvent hydrogenation catalyst of increased activity, wherein the hydrogenation catalyst is produced by reacting ferric oxide with hydrogen sulfide at a temperature range of 260C to 315C in an inert atmosphere to produce an iron sulfide hydrogenation catalyst for the solvent.
Claims: (A) process for hydrogenating coal wherein a coal solvent is hydrogenated in the presence of a hydrogenation catalyst and that hydrogenated solvent in turn hydrogenates the coal ... .
(A) process for hydrogenating coal wherein a coal solvent is hydrogenated in the presence of a hydrogenation catalyst and that hydrogenated solvent in turn hydrogenates the coal, the improvement comprising carrying out the solvent hydrogenation in the presence of an iron sulfide catalyst of increased catalytic activity prepared by the reaction of ferric oxide with hydrogen sulfide ... in a hydrogen atmosphere.
Background and Description: This invention relates to the process for hydrogenating coal and coal solvents in order to recover low molecular weight hydrocarbons. More particularly this invention relates to a method of hydrogenating coal by first hydrogenating a solvent used in the solvent refining of coal. The hydrogenated solvent then donates its hydrogen to the coal material to complete the hydrogenation process. This invention is directed to improved catalysis of this hydrogenation process.
The conversion of coal from a solid hydrogen deficient aromatic based material to a hydrogenated hydrocarbon of low molecular weight has been considered desirable for a long period of time because of the dwindling supplies of petroleum based hydrocarbons in this country and around the world and because of the large reserves of coal known to exist within this country. A process for the conversion of coal solids to liquid hydrocarbons, such as gasoline, would be extremely beneficial.
(If "the conversion of coal" into "gasoline" would have been "extremely beneficial" back in 1987, what, with all that's happened since, would it be today, almost a quarter-century later?)
Various methods for the conversion of coal to hydrocarbons have been suggested by the prior art including the direct conversion of coal by catalytic action and the solvent refining of coal by combined solvent and catalytic action.
This invention is directed to a coal conversion process of the latter type, namely a solvent refined coal recovery process. Particularly, the process involves the production of a catalyst for the hydrogenation of the solvent used in the coal conversion wherein the hydrogenation catalyst is of enhanced activity, of low cost and of no detriment to the depleted coal ash.
The solvent refining or extraction of coal solids is conducted by the contact of an hydrogenated extraction solvent on finely divided coal or other particulate carbonaceous material in an environment of hydrogen gas. This reducing atmosphere hydrogenates and liquefies or depolymerizes the carbonaceous solids of the coal which thereafter become solvated or suspended in the solvent and can be removed from the remaining coal solids or ash for further extraction from the now hydrogen-depleted solvent. This process is enhanced by hydrogenation catalysts. Various expensive hydrogenation catalysts are known for use in coal liquefaction, including palladium, tin, nickel, molybdenum, tungsten and cobalt. These catalysts are used in combinations and can be mounted on alumina carriers. Such catalysts are expensive initially and suffer from process problems in reprocessing or recovery after the catalyst is spoiled by carbonization. Therefore, desirable attributes of a coal liquefaction or hydrogenation catalyst would be inexpensive availability as well as relative abundance. A desirable catalyst should also not impair the coal ash upon which it will contact to avoid problems with the further processing of the coal ash after hydrogenation and liquefaction of the organic portions of coal. The present iron sulfide catalysts meet such criteria.
The present invention provides a process for the hydrogenation of coal and coal liquids in order to provide liquefaction of the solid coal and upgrading of the coal liquids. The process involves the solvent refining of coal wherein the solvent normally constitutes a species of the constituents of the solid coal. The hydrogenation of the coal usually takes place in a two-step sequence in which the coal solvent is first hydrogenated and the hydrogenated coal solvent, in turn, hydrogenates the coal solids. The hydrogenation of the coal solvent is catalyzed, and the improvement of the present invention provides a solvent hydrogenation process wherein a catalyst of increased activity is provided by the reaction of ferric oxide and hydrogen sulfide in a non-oxidizing, atmosphere at a temperature in the range of 260C to 315C.
(We have previously documented the Hydrogen-donating utility of the supposed Coal-use pollutant, Hydrogen Sulfide, in Carbon hydrogenation and conversion processes, as, for just one instance, seen in:
Exxon Methane and Hydrogen from H2S and Carbon Monoxide | Research & Development; concerning: "United States Patent 4,517,171 - Synthesis of H2 and CH4 from H2S and CO; 1985; Exxon Research and Engineering Company; Abstract: Hydrogen and methane are synthesized from a gaseous feed comprising a mixture of H2S and CO";
and, we are compelled to remind you, in passing, that we can obtain the Carbon Monoxide, the "CO", needed for such processes, by, as seen in:
Bayer Improves Coal + CO2 = Carbon Monoxide | Research & Development; concerning: "United States Patent 7,473,286 - Carbon Monoxide Generator; 2009; Bayer Material Science, AG, Germany; Carbon monoxide gas is ... produced ... by means of a continuous process in which carbon-containing raw materials are reacted with oxygen and carbon dioxide".)
The process of this invention is described with reference to the liquefaction and hydrogenation of bituminous coal. However, the invention is deemed to be applicable to the solvent refining of, not only bituminous coal, but other solid carbonaceous materials ... .
The catalysts utilized in the solvent refined coal hydrogenation and liquefaction process of the present invention are produced by the reaction of iron oxides with hydrogen sulfide. This reaction produces an iron sulfide which has been shown to have increased catalytic activity in the hydrogenation of coal solvents. In turn, these coal solvents are utilized to hydrogenate coal solids and effect the liquefaction and recovery of hydrocarbons from the coal.
(And, thus) the present invention provides a superior process for the conversion of coal into hydrocarbons at good yields. The conversion is conducted with the use of uniquely active iron sulfide catalysts which hydrogenate the coal solvent, and in turn, said solvent hydrogenates the coal itself. Therefore, the process involves an improved method utilizing inexpensive catalysts for the production of high yields of hydrocarbons from coal solids and liquids."
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We call your attention to the above-statement of Government Interests, and acknowledgement of "Contract No. DE-AC22-79ET14806 awarded by the U.S. Department of Energy".
For more information concerning that contract, and indication as to why the Air Products and Chemicals Company is the named assignee of rights, we refer you to:
Energy Citations Database (ECD) - - Document #6829488; wherein you can access the details of:
"Evaluation of coal minerals and metal residues as coal-liquefaction catalysts. Final report
Date: February, 1982
Authors: D. Garg, E. Givens, A.R. Tarrer, K. Shridharani, et. al.
Research Organization: Air Products and Chemicals, Inc., PA; and Auburn University., AL
DOE Contract Number: AC22-79ET14806
Abstract: The catalytic activity of various minerals, metallic wastes, and transition metals was investigated in the liquefaction of various coals. The effects of coal type, process variables, coal cleaning, catalyst addition mode, solvent quality, and solvent modification on coal conversion and oil production were also studied. Coal conversion and oil production improved significantly by the addition of pyrite, reduced pyrite, speculite, red mud, flue dust, zinc sulfide, and various transition metal compounds. Impregnation and molecular dispersion of iron gave higher oil production than particulate incorporation of iron. However, the mode of molybdenum addition was inconsequential. Oil production increased considerably both by adding a stoichiometric mixture of iron oxide and pyrite and by simultaneous impregnation of coal with iron and molybdenum. Hydrogenation activity of disposable catalysts decreased sharply in the presence of nitrogen compounds. The removal of heteroatoms from process solvent improved thermal as well as catalytic coal liquefaction. The improvement in oil production was very dramatic with a catalyst".
And, note that we have previously cited the above Garg and Givens several times, as, for one example, in:
Pennsylvania Converts Even More Coal to Liquid Fuels | Research & Development; concerning: "United States Patent 4,411,766 - Iron Catalyzed Coal Liquefaction Process; 1983; Diwakar Garg and Edwin Givens;
Air Products & Chemicals, Incorporated; A process is described for the solvent refining of coal into a gas product, a liquid product and a normally solid dissolved product. Particulate coal and a unique co-catalyst system are suspended in a coal solvent and processed in a coal liquefaction reactor, preferably an ebullated bed reactor. The co-catalyst system comprises a combination of a stoichiometric excess of iron oxide and pyrite which reduce predominantly to active iron sulfide catalysts in the reaction zone. This catalyst system results in increased catalytic activity with attendant improved coal conversion and enhanced oil product distribution as well as reduced sulfide effluent. Iron oxide is used in a stoichiometric excess of that required to react with sulfur indigenous to the feed coal and that produced during reduction of the pyrite catalyst to iron sulfide. The government of the United States of America has rights in this invention pursuant to Contract No. DE-AC22-79ET14806 awarded by the U.S. Department of Energy";
wherein even more US-Patented Coal liquefaction technology is seen to have arisen from the work performed under the same USDOE Contract DE-AC22-79ET14806 that resulted in our primary subject herein: "United States Patent 4,374,016 - Process for Hydrogenating Coal and Coal Solvents".
And, finally, in closing, we'll note that all of the above work performed, and achievements made, under that such productive USDOE Contract DE-AC22-79ET14806 were apparently so encouraging to our United States Department of Energy that they subsequently issued another contract for advanced development of the same sorts of Coal liquefaction technology, as seen via:
Energy Citations Database (ECD) - - Document #5989547; which link connects with:
"Solvent Tailoring in Coal Liquefaction; Final Report
Date: January, 1984
Author: A.R. Tarrer, et. al.
Research Organization: Auburn University, AL. Coal Conversion Lab
USDOE Contract Number: FG22-80PC30209; Report Number: DOE/PC/30209-T12
Abstract: The key to better and more effective coal liquefaction may be in proper tailoring of the coal liquefaction recycle solvent. The objective of this work is to investigate various factors which contribute to the solvent effectiveness as a coal liquefaction agent. Particular emphasis is placed on the critical solvent properties and on critical properties of solvent mixtures. The liquefaction process solvent serves a three-fold purpose: it acts as a solvent for soluble fractions and products; it influences the liquefaction reactions, e.g., as a donor of hydrogen to free radicals formed by thermal rupture of chemical bonds; and it acts as a carrier fluid for feed coal and for reaction products. One purpose of this work is to develop an understanding of how to utilize this interaction to accelerate liquefaction kinetics and improve product selectivity."
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Now, we've been conditioned to accept the fact that the pointed questions and sometimes-derisive comments we often cannot help ourselves from interjecting in our reports aren't much appreciated, but:
Herein we have clear and irrefutable proof of the fact that our United States Government used our tax money to pay a well-known Pennsylvania corporation, Air Products, and a fabled southern university, Auburn, who are a partner, with WVU, in the Consortium for Fossil Fuel Science, to develop a full suite of Coal conversion technologies which would, better than three decades ago, have enabled us to start converting our abundant Coal into a wide variety of seemingly-useful things, such as "a gas product" and "a liquid product", and, which "liquid product" could be, as suggested by Auburn, "liquid hydrocarbons, such as gasoline".
And, that proof was published by our own United States Government in all the instances we cite herein well more than one quarter of a century ago.
When, do you suppose, the art and science of reporting news of importance to the citizens of US Coal Country - - news such as that concerning the fact our own US Government confirms that our abundant domestic Coal can be efficiently converted into, among other needful things, "gasoline" - - will become as advanced and well-developed as that art and science, for converting Coal into Gasoline, itself actually is?