WV Coal Member Meeting 2024 1240x200 1 1

Oklahoma & New Jersey Direct Hydrogenation of WV & PA Coal

United States Patent: 3960700

This will be a somewhat lengthy dispatch; but, the references we include document the sequential, methodical development of a Coal hydrogenation technology, intended to efficiently convert Coal into liquid and gaseous hydrocarbons, that seems to us so integrated that reporting on each individual component separately wouldn't do justice to the work.

First, we remind you that the use of elemental, molecular Hydrogen for the hydrogenation of Coal, to form hydrocarbon liquids and gases, affords both efficiencies in the process and a better mix of hydrocarbons thus produced.

An example of our reportage documenting that fact can be accessed via:

California Rocket Scientists Liquefy Coal | Research & Development; which includes information concerning, among other, similar, examples:

"United States Patent 4,243,509 - Coal Hydrogenation; 1981; Rockwell International Corporation, CA; Abstract: Disclosure is made of a method and apparatus for reacting carbonaceous material such as pulverized coal with heated hydrogen to form hydrocarbon gases and liquids suitable for conversion to fuels wherein the reaction involves injection of pulverized coal entrained in a minimum amount of gas and mixing the entrained coal at ambient temperature with a separate source of heated hydrogen. The heated hydrogen and entrained coal are injected through a rocket engine type injector device. The coal particles are reacted with hydrogen in a reaction chamber downstream of the injector. The products of reaction are rapidly quenched as they exit the reaction chamber and are subsequently collected."

The use of Hydrogen in such a way would seem to more than justify the expense of obtaining the Hydrogen, especially since, as seen in:

Germany Makes Economical Hydrogen from H2O | Research & Development; concerning:

"United States Patent Application 20090026089 - System and Method for Splitting Water; 2009; Hermsdorfer Institut, Germany; Abstract: The present invention relates to a system and a method for cleaving water by means of hyperpolarisation, the system comprising a first electrode and at least one additional electrode; at least one porous ferroelectric layer arranged between the first and the additional electrode; as well as an AC voltage or pulsed DC voltage source. With the method according to the present invention it is possible to cleave the water economically into hydrogen and oxygen and obtain gases for technical purposes";

and, as we will be documenting further, the ways and means for obtaining elemental Hydrogen are being further refined and made much more practical.

Further, the use of elemental Hydrogen in Coal conversion processes enables some interesting "twists" to be added to the procedure, as seen in:

More Oklahoma CO2 + Coal = Hydrocarbon Syngas | Research & Development | News; concerning: "United States Patent 4.040,976 - Process of Treating Carbonaceous Material with Carbon Dioxide; 1977; Cities Service Company, OK; Abstract: A mixture of carbon dioxide and a carbonaceous material, such as coal, is rapidly heated in a reactor, giving a gaseous effluent comprising carbon monoxide. If hydrogen is added with the feed stream, a CO--H2 mixture is produced";

where the use of Hydrogen to hydrogenate Coal enables the inclusion of Carbon Dioxide, recovered from whatever source, into the mix or reactants; where it, too, is converted with the Coal into a hydrocarbon synthesis gas suitable for catalytic condensation into liquid hydrocarbon fuels. .

Herein, we see that the above-cited "United States Patent 4.040,976" was actually just one of the direct Coal hydrogenation technologies established by the old "Cities Service Company", later known as "Citgo", which, back in the 1980's, fell victim to the corporate takeover mania, with bits of it, ultimately, winding up in the hands of Occidental Petroleum and the nationalized petroleum company: "Petroleos de Venezuela".

In any case, we see herein, via a sequence of six United States Patents, how Cities Service developed and established a comprehensive technology for the direct hydrogenation of Coal with elemental Hydrogen.

First up, as accessed via the initial link in this dispatch, we present necessarily-brief excerpts from:

"United States Patent 3,960,700 - Coal Hydrogenation to Produce Liquids

Date: June, 1976

Inventor: Bernard Rosen, et. al., NJ

Assignee: Cities Service Company, OK

Abstract: Crushed coal is mixed with hot hydrogen, at 500 to 1,500C. and 600 to 3,000 psig., in a reactor, and then, after a short reaction time, rapidly quenched. The total heat-up, reaction, and quench time is less than 2 seconds. This short residence time results in less gas production and less polymerization of the liquid components.

Claims: A process of treating carbonaceous material with hydrogen, in the absence of added catalyst, (and, a) method of converting coal into liquid hydrocarbon ... .

Background and Summary: This invention concerns coal hydrogenation. More particularly, it concerns a process for treating coal with hydrogen, in the absence of any added catalyst and/or solvent, to obtain a maximum of desirable liquid hydrocarbon and a minimum of gaseous and polymerized products. The utility of the invention resides in the production of desirable hydrocarbons from coal.

We believe that we have overcome, or greatly reduced, the disadvantages of prior art processes by our process of treating carbonaceous material with hydrogen, in the absence of added catalyst, with the process comprising the serial steps of (a) adding crushed carbonaceous material to a reactor, (b) adding hot hydrogen to the stream of carbonaceous material, (c) reacting the hydrogen and the carbonaceous material for a period of from about 2 milliseconds to less than 2 seconds, and (d) quenching the mixture within the reactor. In a narrower aspect, the invention concerns a method of converting coal into liquid hydrocarbons."

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Again, we keep our excerpts brief since we have a lot of ground to cover. However, we must note, that, even though valuable hydrocarbons are produced directly and at great speed, depending upon the grade of Coal and the sorts of other materials, aside from Carbon, it contains; some significant quantities of other compounds, such as Ammonia, NH4, and even some relatively small amount of CO2, are also co-produced.

However, both of those, as we've documented now in many other reports, can be treated and utilized as valuable byproducts.

In any case, "United States Patent 3,960,700" was followed shortly by:

"United States Patent: 3997423 - Short Residence Time Low Pressure Hydropyrolysis of (Coal)

Date: December, 1976

Inventor: Marvin Greene, NJ

Assignee: Cities Service Company, OK

Abstract: Crushed coal is mixed with hot hydrogen, at 500 to 1,500C and 0 to 250 psig., in a reactor, and then, after a short reaction time, rapidly quenched. The total heat-up, reaction, and quench time is less than 2 seconds. This short residence time results in a high yield of coal tars.

Claims: A process of treating carbonaceous material with hydrogen, in the absence of added catalyst, to produce a yield of carbonaceous tars.

Background: This invention concerns coal liquefaction. More particularly, it concerns a process for treating coal with hydrogen, in the absence of any added catalyst and/or solvent, to obtain a high yield of coal tars. The utility of the invention resides in the production of high yields of desirable long chain aromatic hydrocarbons from coal.

 

Our process, involving, at low pressure, short heat-up and quench times, results in improved yields of desirable tar products, no problems of catalyst addition or removal, simplified apparatus, and improved process reliability."

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Note, that, in the above, a greater amount of "tar products" are generated, which, as we will see, genuinely are, as Cities Service puts it, "desirable".

"United States Patent 3,997,423" was then followed very shortly by the very similar, closely-related:

United States Patent: 4003820 - Short Residence Time Hydropyrolysis of Carbonaceous Material

Date: January, 1977

Inventor: Arnold Pelofsky, et. al., NJ

Assignee: Cities Service Company, OK

Abstract: A process for treating carbonaceous material with hydrogen including adding the carbonaceous material into a first reaction zone of a reactor having at least two reaction zones; adding hot hydrogen to the stream of carbonaceous material to effect a reaction with same to produce reaction products; quenching the mixture while insuring that the total residence time varies from about 2 milliseconds to about 2 seconds; removing at least a portion of the reaction products from the quenched mixture; and introducing the residual carbonaceous material into a subsequent reaction zone and repeating the steps for the subsequent reaction zone.

Claims:  A process for converting coal into fluid hydrocarbons.

Background and Filed: This invention relates to coal hydrogenation. More particularly, it relates to a process for treating coal with hydrogen, in the absence of added catalyst and/or solvent, to obtain a maximum of desirable liquid hydrocarbon in a minimum of gaseous and polymerize products. The utility of the invention resides in the production of desirable hydrocarbons from coal";

and:

"United States Patent: 4012311 - Short Residence Time Low Pressure Hydropyrolysis of (Coal)

Date: March, 1977

Inventor: Marvin Greene, NJ

Assignee: Cities Service Company, OK

Abstract: A process for treating carbonaceous material with hydrogen at low pressure including adding the carbonaceous material into a first reaction zone of a reactor having at least two reaction zones; adding hot hydrogen to the stream of carbonaceous material to effect a reaction with same to produce reaction products; quenching the mixture while insuring that the total residence time varies from about 2 milliseconds to about 2 seconds; removing at least a portion of the reaction products from the quenched mixture; and introducing the residual carbonaceous material into a subsequent reaction zone and repeating the steps for the subsequent reaction zone.

Claims: A process for treating carbonaceous material with hydrogen, in the absence of added catalyst, to produce a high yield of carbonaceous tars.

Background and Field: This invention relates to coal hydrogenation. More particularly, it relates to a process for treating coal with hydrogen, in the absence of added catalyst and/or solvent, to obtain a high yield of coal tars.

The utility of the invention resides in the production of desirable long chain aromatic hydrocarbons from coal.

Feed material for the process broadly includes carbonaceous material, exemplified by coal (and) organic waste."

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Aside from the Carbon-recycling aspect of utilizing, in addition to Coal, "organic waste", Cities Service also more fully explains that the advantages of the above processes include lower operating pressures and temperatures, and thus lower energy demands; and, that no catalyst is required, with the extra expense that might otherwise entail.

Again, the "tars" produced from Coal, by the above processes are "desirable" since they can, subsequently, be further refined, as seen in:

"United States Patent: 4013543 - Upgrading Solid Fuel-Derived Tars Produced by ... Hydropyrolysis

Date: March, 1977

Inventor: Marvin Greene, NJ

Assignee: Cities Service Company, OK

Abstract: Crushed carbonaceous fuel is rapidly mixed with hot hydrogen, at 500 to 1,500C and 0 to 250 psig., in a reactor, and then, after a short reaction time, rapidly quenched. The total heat-up, reaction, and quench time is less than 2 seconds. This short residence time and rapid heat-up results in a high yield of carbonaceous tars. The carbonaceous tars are subsequently and directly introduced into a fluid coker to obtain gas, upgraded carbonaceous tars, and hot coke.

Background and Field: This invention is related to carbonaceous tars. More particularly, this invention concerns a method of producing and upgrading coal tars which have been produced from a process for treating coal with hydrogen, in the absence of any added catalyst and/or solvent.

My process, involving, at low pressure, short heat-up and quench times, results in improved yields of desirable tar products, for upgrading with fluid coking, no problems of catalyst addition or removal, simplified apparatus, and improved process reliability."

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We will note that the process of "United States Patent 4,013,543" concerns itself with both the upgrading of Coal tar generated by the hydropyrolysis and of more processing of the Coal itself; and, that "fluid coking" is a standard type of petroleum refining process designed and intended to extract more hydrocarbon values from tarry, carbonaceous "resids".

There is nothing in the above that wouldn't be unfamiliar to your average petroleum engineer. Cities Service is making their technology for converting Coal, and "organic wastes", into "upgraded tars" that would be very similar to conventional petroleum intermediate products.

And, finally, we conclude with an example of Cities Service Coal conversion technology that points directly to where all of this should be headed, as in:

"United States Patent: 4411871 - Apparatus for Converting Coal

Date: October, 1983

Inventors: Arthur Gulbrandsen and Uriel Oko, OK

Assignee: Cities Service Company, Tulsa

Abstract: An apparatus, for the rapid heating and subsequent reaction of carbonaceous material and hydrogen, comprising a cylindrical reactor shell; a first inlet conduit, coaxial with the shell, terminating inside the shell and having the terminal discharge end covered with a metal that resists carbide formation which leads to plugging; a second inlet conduit whose discharge end is in proximity to the discharge end of the first conduit; and suitable insulation means between the first and second conduits.

Claims:  A reactor for the rapid heating of carbonaceous materials and hydrogen and the subsequent reaction thereof (as described and specified).

Background: This invention concerns the processing of carbonaceous materials. More particularly, it concerns the conversion of coal into by-products. It further concerns the conversion of caking coal into liquid products. A particular utility of the invention resides in its use in the hydropyrolysis of caking coal to produce desirable liquid products.

Summary: We believe that our invention prevents or greatly reduces the possibility of agglomeration of particles of carbonaceous materials, exemplified by coal, when the materials are fed to a high-pressure, high-temperature reactor, without the necessity of high particle velocity or high turbulence.

We have found that (our) method and apparatus for converting coal into desirable by-products prevent or markedly reduce the occurrence of agglomeration or the formation of plugs due to agglomeration ... .

Thus there is an increased flexibility in the choice of coals to be processed, and a reduction in maintenance and down-time.

The invention is concerned with the results obtained during and from the heating of carbonaceous materials. (which) include peat, lignite, coal, solvent refined coal (and) wood shavings, ... the typical material being coal. There are various types of coal, frequently classified as being "caking" or "noncaking," as mentioned earlier. The invention is operable with all these carbonaceous materials. 

Representative examples of agglomerating coals are found in Eastern United States, such as West Virginia, Kentucky, Illinois and Pennsylvania."

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And, make no mistake: the entire purpose of these processes for converting Coal, as in "United States Patent 4,003,820", "into desirable ... fluid hydrocarbons", developed as they were in Oklahoma and New Jersey, is to make such conversions especially efficient when applied to the abundant "coals" of the type "found in ... West Virginia, Kentucky, Illinois and Pennsylvania".

We have, of course, abbreviated the Disclosures of these technologies in the extreme; and, the full documents and technical details are worthy of study by anyone genuinely interested.

But, we must ask:

How is it they knew, fully three decades ago, in Oklahoma and New Jersey, that it was worth applying an obviously concerted effort, by multiple laboratories and multiple scientists, into developing better and more efficient ways of converting Coal, from, especially, "West Virginia, Kentucky, Illinois and Pennsylvania", "into desirable fluid hydrocarbons" and, as in "United States Patent 4,012,311", "desirable long chain aromatic hydrocarbons"; but, those of us resident in "West Virginia, Kentucky, ...and Pennsylvania", have - - for the most part, even when we're paying $3.50 a gallon for lower grade gasoline, with most of that $3.50 flowing into the purses of foreign nation oil sheiks and the coffers of multinational Big Oil companies - - never even given the conversion of our abundant Coal, and even some of our Carbon-recycling and renewable "organic wastes" and "wood", into that gasoline, a second, passing thought?

Maybe it is that not very many people, at all, in "West Virginia, Kentucky, ...and Pennsylvania", actually know anything about the truth of the matter, that we can efficiently make "hydrocarbons" from Coal.