Hydrogenolysis of coal hydrogenation products
In several previous reports, dating back now a few years, we've documented the late-1950's, early-1960's operation, by the former Union Carbide Corporation, since assimilated into Dow Chemical, of a Coal liquefaction and hydrogenation factory in South Charleston, West Virginia.
And, in fact, an interesting compilation concerning Union Carbide's Coal conversion operations in Charleston can be found in the West Virginia Division of Culture and History's own West Virginia State Archives, via:
Union Carbide Corporation Collection; which contains, for one example, the report: "Union Carbide Corporation: The Coal Hydrogenation Program and Related Coal Projects. Compiled and Edited by John J. Potter, Jr., October 1995".
We remain uncertain, due to lack of precise documentation, of when Carbide's South Charleston Coal hydrogenation facility actually ceased operation; but, we believe it to have been, again, in the early 1960's.
However, we have documented that their interest in Coal conversion technology continued for quite a few decades afterwards, as seen in our previous reports of:
Charleston, WV, Coal + Steam = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 3,988,237 - Integrated Coal Hydrocarbonization and Gasification of Char; 1976; Inventors: Hubert Davis, Charles Albright, et. al.; all of West Virginia; Assignee: Union Carbide Corporation, NY;
Abstract: An integrated continuous process for the production of liquid and gaseous fuels"; and:
WV Union Carbide Purifies Coal Syngas | Research & Development; which makes report of: "United States Patent 4,740,361 - Removing Metal Carbonyls from Gaseous Streams; 1988; Inventor: Robert Heyd, Morgantown, WV; Assignee: Union Carbide Corporation; Abstract: Process for removing metal carbonyl contaminants from ... synthesis gas (which is) a gas mixture containing primarily hydrogen and carbon monoxide (and which) can be produced by the ... gasification of coal".
Herein, via the initial link in this dispatch, we demonstrate that Union Carbide, in West Virginia, wasn't just synthesizing crude liquid hydrocarbons from Coal back in the 1950's, but, they were also developing the technology to refine those crude Coal liquids into direct substitutes for petroleum-derived fuels and oils.
And, in so doing, they demonstrated a fact we have, from other sources, already documented:
Coal liquids can be processed into standard liquid hydrocarbon fuels and petrochemicals through conventional and long-established petroleum refinery techniques.
And, those standard petroleum refinery techniques don't in all cases utilize a great deal of catalyzed finesse in their functions.
In some cases, at least, it's just a question of squeezing the juice hard enough and heating it high enough.
Comment, and some additional reference links, follows, and is inserted within, our excerpts from the initial link in this dispatch to:
"United States Patent 2,913,397 - Hydrogenolysis of Coal Hydrogenation Products
Date: November, 1959
Inventors: James Murray, et. al., South Charleston and Nitro, WV
Assignee: Union Carbide Corporation, NY
Abstract: This application relates to chemical processes. More particularly it relates to an improvement in processes for obtaining chemicals from coal.
Various processes have been proposed for the purpose of obtaining chemicals from coal. Among the most promising of these have been those involving coal hydrogenation.
Broadly speaking, such processes encompass contacting coal with hydrogen in such a manner that the coal is converted to gaseous and liquid products, plus a pitch residue, and in most instances a small amount of ash. While such processes have made available a vast number of chemicals from coal, the very prolificacy of these processes, in terms of chemical compounds produced thereby, has raised the problem of separating these compounds, which is highly important to the economic feasibility of the entire coal hydrogenation process.
Our present improvement is directed to a hydrogenolysis of coal hydrogenation products, whereby the individual compounds comprising such products are de-alkylated and.or aromatized to compounds of simpler structure which can be readily separated and recovered.
In the process of the invention the material to be processes, as for example the liquid product of coal hydrogenation, is subjected to reaction with hydrogen at elevated temperatures and under increased pressure, in the absence of a catalyst, for the purpose of achieving the desired hydrogenolysis and consequent simplification of the product.
Among the coal hydrogenation products to which the invention is applicable is the liquid and semi-liquid portion of the whole product of the coal hydrogenation process, including the pitch, after removal of the gaseous constituents and the ash.
Such a coal hydrogenation liquid product with its 200 or more usual constituents is conveniently divided by boiling temperature range into three main fractions or categories.
The first is a light oil fraction which ... contains a large number of ring compounds (which, after some purification) is commonly known as neutral light oil (and is) comprised predominantly of benzene and naphthalene ... .
(Keep in mind, that, as seen in our earlier report of:
WVU Hydrogenates Coal Tar | Research & Development; concerning: "Hydrogenation of Naphthalene and Coal Tar Distillate; Abhijit Bhagavatula; West Virginia University; 2009; Abstract: The hydrogenation of naphthalene (to) the hydrogenated product, tetralin";
such "naphthalene" is the base material used to make "tetralin", the Hydrogen donor solvent specified by WVU in their "West Virginia Process" for the direct liquefaction of Coal.)
The second major fraction of the coal hydrogenation product is commonly referred to as the middle oil ... .
A third major fraction of liquid product of coal hydrogenation is referred to as heavy oil.
Yet another fraction of the coal hydrogenation liquid product is semi-liquid pitch.
It is therefore an object of the invention to provide an improvement in coal hydrogenation processes whereby a product is obtained having a high proportion of highly aromatic ... compounds, which may be readily separated from one another ... by such methods as fractional distillation.
According to the process of our invention ... a product is obtained which is rich in unsubstituted and methyl and ethyl substituted aromatic compounds by subjecting the liquid product of coal hydrogenation, including the pitch, to hydrogen pressure of more than 1000 pounds per square inch ... at a temperature above 525 C and in the absence of a catalyst."
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We'll end our excerpts there since the remaining bulk of the disclosure is devoted to the complexities of separating different hydrocarbon product streams from the "hydro-cracked" Coal liquids.
This Carbide technology does require, just as do many conventional petroleum refineries, a supply of elemental, molecular Hydrogen for the "cracking" process. And, conventional petroleum refineries do have their own ways of getting that Hydrogen.
But, we submit that a technology such as that seen in our report of:
H2 for Coal Hydrogenation from Coal Gasification By-Product | Research & Development; concerning: "United States Patent 4,693,883 - Ammonia Utilization Process; 1987; Assignee: Institute of Gas Technology, Chicago; An ammonia utilization process substantially eliminates by-product ammonia gas produced during hydrogen forming gasification processes by recycling sour water stripper off-gas comprising ammonia to a hydrogen forming gasifier wherein by-product ammonia gas is converted to desired hydrogen product gas and nitrogen";
wherein ammonia is co-produced during an initial Steam, H2O, gasification of Coal, as a way of "contacting coal with hydrogen in such a manner that the coal is converted to gaseous and liquid products, plus a pitch residue", as in the process of our subject "United States Patent 2,913,397"; and, wherein less-expensive air is used instead of expensive purified Oxygen in that initial Steam gasification; that ammonia can then be broken down via the above process of "US Patent 4,693,883", and, thus be made to supply at least some of the Hydrogen required by the West Virginia Union Carbide process, for their "hydrogenolysis of coal hydrogenation products" to form the desired "methyl and ethyl substituted aromatic compounds";
might be appropriate for use in US Coal Country.
And, yes, the pressures and temperatures, specified by Union Carbide, seem quite high; almost as if the only way to convert raw Coal liquids into petroleum product substitutes was by applying an impractical amount of "brute force".
But, via:
Kobelco - Applications - Oil Refinery; we can learn that conventional Oil refinery Hydrogen pressures under 1,500 pound per square inch are considered to be only "mid-range" for standard petroleum refining applications. So, the "more than 1000 pounds per square inch" of Hydrogen pressure required herein by Union Carbide is well within the limits of established and conventional petroleum refinery technology.
And, via:
Cracking (chemistry) - Wikipedia, the free encyclopedia; we can learn that temperatures well above Union Carbide's specified "525 C", even up to and "between 660 C to 760 C", are commonly employed in conventional petroleum refinery "cracking" operations to break down "high molecular weight oil".
So, nothing out of the ordinary, as far as petroleum refining science and technology is concerned, is needed to, as specified herein by a team of scientists cloistered in and around the capitol city of West Virginia, convert raw, hydrogenated liquids, made by a process obviously more than half a century old, out of Coal, along with the still-carbonaceous residue, the "pitch", remaining after that initial hydrogenation and extraction of oils from Coal, into a variety of petroleum-type liquid hydrocarbons, all of which could serve to help displace and replace any and all of the products we now allow ourselves to be economically enslaved to Big Oil, and forced to kiss the ring of OPEC, for the supply of.
Far past time an end was put to all of that, ain't it?