United States Patent: 4994498

We've many times documented the plain fact, that, at one time, for a number of decades, Coal was being efficiently converted into liquid fuels just down and across the Kanawha River from, perhaps almost in sight of, the West Virginia State Capitol Building.

Union Carbide Corporation, at a couple of sites near and around Charleston, WV, starting in the late 1950's and even up until the early 1990's, prior to their assimilation by, in 2001 we believe, Dow Chemical Company, devoted a seemingly concentrated effort into demonstrating that Coal could be efficiently converted into a wide variety of hydrocarbons, which hydrocarbons included, even, synthetic rubber.

As we've previously informed you, a compilation of Union Carbide's Charleston-area Coal conversion achievements can be found in a big box in the basement of the building where the official West Virginia State Archives are housed.

Those reports aren't accessible online; but, if any interested-enough journalists still know how to tear themselves away from their computer screens, get off their fannies and go do a little actual research, here are some links that can tell you where to go and what to look for:

At the: West Virginia Division of Culture and History, you'll be looking for the "Archives Library", which is located in the Culture Center at the State Capitol Complex in Charleston.

In the Archives Library, you'll be looking for the Union Carbide Corporation Collection; which is organized into two "boxes".

In Box 1, you want to root out a folder, or folio, entitled:

"Union Carbide Corporation: The Coal Hydrogenation Program and Related Coal Projects. Compiled and Edited by John J. Potter, Jr., October 1995".

That folder might contain some nearly-ancient gems, such as, for instance, more information on technologies now more than half-a-century old, like that seen, for just one example, in our report of:

West Virginia Coal Association | West Virginia Hydrocracks Coal Liquids with Brute Force | Research & Development; concerning: "United States Patent 2,913,397 - Hydrogenolysis of Coal Hydrogenation Products; 1959; Inventors: James Murray, et. al., South Charleston and Nitro, WV; Assignee: Union Carbide Corporation; Abstract: This application relates to ... an improvement in processes for obtaining chemicals from coal".

And, it might also provide background on how Carbide's West Virginia Coal conversion development efforts continued, inexplicably unknown to, and unacknowledged by, the general public, as seen, for example, in:

West Virginia Coal Association | West Virginia 1982 Coal to Ethanol | Research & Development; concerning: "United States Patent 4,333,852 - Production of Ethanol and Methanol Directly from Synthesis Gas; 1982; Inventor: Barbara Warren, Charleston, WV; Assignee: Union Carbide Corporation; Abstract: Alkanols are selectively produced as the major product directly from synthesis gas";

throughout several following decades.

Now, we know that Union Carbide was, of course, in the Charleston area, making their "synthesis gas" blend of Carbon Monoxide and Hydrogen out of Coal; but, we confess that we have yet to find a formal description of their own Coal gasification technology. And, we speculate that they might just have been employing a Coal gasification process developed, again more than half a century ago, by one of their major corporate Charleston, West Virginia, neighbors, such as that seen in:

West Virginia Coal Association | WV 1955 Hydrogen & Syngas from Coal | Research & Development; concerning: "United States Patent 2,699,384 - Carbon Monoxide and Hydrogen from Carbonaceous Solids; 1955; Inventors: Luther Perry, et. al., Charleston, WV; Assignee: E.I. DuPont and Company; Abstract: This invention ... is more particularly directed to the preparation of hydrogen ... and gaseous mixtures containing hydrogen and carbon monoxide (from) coal. An object of this invention is to provide an improved process for the preparation of synthesis gas from coal (which will contain) principally carbon monoxide (and) hydrogen ... wherein the ratios of the constituents can be accurately controlled. We claim: ... a process for the preparation of carbon monoxide and hydrogen by the partial combustion of coal in the presence of steam".

And, we document herein that Union Carbide, in Charleston, continued, subsequent to their above-cited "United States Patent 4,333,852 - Production of Ethanol and Methanol Directly from Synthesis Gas", to improve their West Virginia-born technology for indirectly converting our abundant Coal into those versatile, and profoundly valuable, alcohols.

As seen in excerpts, with comment inserted and appended, from the initial link in this dispatch to:

"United States Patent 4,994,498 - Tantalum-containing Catalyst for Producing Alcohols from Synthesis Gas

Date: February, 1991

Inventor: Nancy Kinkade, Charleston, WV

Assignee: Union Carbide Chemicals and Plastics Company, CT

Abstract: A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

Government Interests: The Government of the United States has rights in the invention pursuant to Contract No. DE-AC 22-86PC90013 awarded by the U.S. Department of Energy

(Concerning the above "molybdenum sulfide", according our the US Geologic Survey, as seen via:

http://minerals.usgs.gov/minerals/pubs/commodity/molybdenum/mcs-2011-molyb.pdf; "In 2010, molybdenum, valued at about $885 million (based on average oxide price), was produced by eight mines. Molybdenum ore was produced as a primary product at three mines—one each in Colorado, Idaho, and Nevada—whereas five copper mines (three in Arizona, one each in Montana and Utah) recovered molybdenum as a byproduct";

we seem to have significant domestic production potentials. However, when it comes to "tantalum", as in:

USGS Minerals Information: Niobium (Columbium) and Tantalum;

we have little of it accessible in the United States itself, but, secure supplies of it could be provided by our  Canadian cousins. Our friends in Australia and Brazil have plenty, as well.

Keep in mind, too, that the molybdenum and the tantalum serve only as catalysts; and, aren't used up or consumed to any appreciable extent in the process. Their purchase would thus represent more of a capital, rather than an operating, expense.)

Claims: A process for producing a mixture of lower alkanols comprising reacting hydrogen and carbon monoxide in the vapor phase in the presence of a catalyst consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound in an amount of at least about 0.20 mole of alkali metal per mole of molybdenum, and a tantalum compound in an amount of at least about 0.3 mole of tantalum per 100 moles of molybdenum. 

The process ... wherein the alkali metal compound is selected from organic and inorganic salts, oxides, sulfides and hydroxides of alkali metals (and) wherein said inorganic salt is potassium acetate. 

The process ... wherein the molar ratio of CO:H2 is from 2:1 to 1:4.

(This system is, thus, very tolerant of synthesis gas of widely-varying composition. As we have in other reports documented, it is more usually preferred that the "ratio of CO:H2" be closer to 1:2. However, as in our above-cited process of "US Patent 2,699,384 - Carbon Monoxide and Hydrogen from Carbonaceous Solids", "wherein the ratios of the constituents can be accurately controlled"; and in others similar, it is clearly indicated that the "ratio of CO:H2" in the product syngas can be controlled and adjusted, if needed, by varying the relative amounts of Steam and Coal fed into the initial gasification process.) 

The process ... wherein the temperature of reaction is from 250 C to 400 C.

(Since the reactants themselves will be emerging from the partial oxidation, or limited combustion, as it were, of Coal, maintaining those temperatures shouldn't require the input of any additional energy.)

The process ... wherein the catalyst is obtained by decomposing a tantalum-impregnated tetrathiomolybdate salt to obtain tantalum-impregnated molybdenum sulfide and then adding the alkali metal compound to said tantalum-impregnated molybdenum sulfide.

(There are, apparently, some "tricks" to actually preparing the catalyst, which add value.)

The process ... wherein the tantalum compound is present in the catalyst in an amount to provide from 0.3 mole to 10 moles of tantalum per 100 moles of molybdenum.

(Thus, the more difficult-to-get "tantalum" is needed only in minor quantities relative to the more abundant, domestically-available, "molybdenum".)

Background and Description: This invention relates to a catalytic process for producing alcohols directly from carbon monoxide and hydrogen.

More particularly, the present invention pertains to a tantalum and alkali-containing molybdenum sulfide heterogeneous catalyst and to its use for converting carbon monoxide and hydrogen to alcohols. 

Almost as old as the Fischer-Tropsch process for making hydrocarbons is the Fischer-Tropsch process for making alcohols. The reaction is carried out by passing a mixture of carbon monoxide and hydrogen over a catalyst for the hydrogenation of the carbon monoxide.

Molybdenum-based catalysts have ... been used to catalyze a variety of reactions such as desulfurization, denitrification and hydrogenation reactions.

(We interrupt to note that molybdenum is frequently specified as a catalyst both in similar and in only more broadly-related Coal conversion process technologies, as, for one example, seen in:

West Virginia Coal Association | Exxon Liquefies More Coal with Coal Oil and Sulfur | Research & Development; concerning: "US Patent 4,111,787 - Staged Hydroconversion of an Oil-Coal Mixture; 1978; 
Exxon Research and Engineering Company; Abstract: A catalytic slurry hydroconversion process for producing normally liquid hydrocarbons from a heavy hydrocarbonaceous oil and from coal wherein (the specified) oil soluble metal compound ... is molybdenum naphthenate", or, in other words, a Coal oil, i.e., Naphthalene, salt of molybdenum.)

In accordance with the present invention, mixtures of alcohols are produced by reacting carbon monoxide and hydrogen over a heterogeneous catalyst consisting essentially of an intimate mixture of molybdenum sulfide, a significant amount of a compound of an alkali metal and a tantalum compound. 

In a first aspect, the present invention pertains to a process which comprises reacting carbon monoxide and hydrogen in the vapor phase, in the presence of a heterogeneous catalyst consisting essentially of molybdenum sulfide, an alkali metal compound and a tantalum compound to produce ... alcohols at a high rate.

The carbon monoxide and hydrogen reactants may conveniently be derived from synthesis gas which is primarily a mixture of carbon monoxide and hydrogen. Depending on its source, the reactant feed may typically contain a very small amount of sulfur compounds as well as small amounts of carbon dioxide, and nitrogen and other inert gases.

Synthesis gas is produced commercially, for example, as a product of the partial combustion of coal."

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And, that seems a particularly apt place to close our excerpts.

In sum, we can, via an initial gasification of Coal, accomplished using long-established, well-known, efficient technology, and the subsequent catalytic chemical condensation of the synthesis gas thus produced, as fully disclosed by the West Virginia-developed technology of our subject herein, "United States Patent 4,994,498 - Tantalum-containing Catalyst for Producing Alcohols from Synthesis Gas", produce both Ethanol and Methanol.

Those two alcohols, we affirm, are valuable raw materials which can be utilized in a number of commercial industrial processes to manufacture a variety of important and needed products.

However, of perhaps most interest to us all in the context of this report is the fact, that, as seen in:

West Virginia Coal Association | Mobil Oil 1977 Coal-Derived Alcohols to Gasoline | Research & Development; concerning: "United States Patent 4,025,575 - Process for Manufacturing Olefins; 1977; Assignee: Mobil Oil Corporation; Abstract: A lower alcohol ... feed is selectively converted to a mixture of light olefins, including ethylene and propylene, by catalytic contact of the feed ... with certain crystalline aluminosilicate zeolite catalysts exemplified by HZSM-5. (A) method for converting a feed to light olefins, said feed comprising ... methanol or ... ethanol";

once we have the Methanol and the Ethanol, as made so efficiently by the West Virginia process of our subject herein, "United States Patent 4,994,498 - Tantalum-containing Catalyst for Producing Alcohols", out of synthesis gas derived from Coal, we can convert those Coal-derived Alcohols into a wide range of liquid hydrocarbons, including those used in the making of plastics, and in the blending of Gasoline.


West Virginia Coal Association - PO Box 3923 - Charleston, WV 25339 | 304-342-4153 | website developed by brickswithoutstraw