United States Patent: 4207208

We have many times made reference to ExxonMobil's "MTG"(r), methanol-to-gasoline, technology, wherein the methanol is posited to be made from Coal.

We have also documented their specification and use of a specific "zeolite" mineral, most often designated as "ZSM-5", as the preferred catalyst, or catalyst carrier, for such Coal conversion processes.

Herein, we learn that We The People footed the bill for ExxonMobil to figure at least some of their ZSM-5, Coal-based MTG(r), technology out.

 

Comment follows excerpts from:

 

"United States Patent 4,207,208 - Activity Improvement of Syngas Conversion Catalyst

 

Date: June, 1980

 

Inventors: Stanley Lucki, et. al., NJ

 

Assignee: Mobil Oil Coporation, NY

 

Abstract: A method is disclosed for the treatment of single particle iron-containing syngas (synthesis gas) conversion catalysts comprising iron, a crystalline acidic aluminosilicate zeolite (as specified). The catalyst does not contain promoters and the treatment is applicable to either the regeneration of said spent single particle iron-containing catalyst or for the initial activation of fresh catalyst. The treatment involves air oxidation, hydrogen reduction, followed by a second air oxidation and contact of the iron-containing single particle catalyst with syngas prior to its use for the catalytic conversion of said syngas. The single particle iron-containing catalysts are prepared from a water insoluble organic iron compound.

Government Interests: The Government of the United States of America has rights in this invention pursuant to Contract No. E(49-18)2276 awarded by the U.S. Energy Research and Development Administration.

Claims: A method for treating either a fresh or spent single particle iron-containing syngas conversion catalyst composition prepared by forming a mixture of a water insoluble iron derivative of an organic compound, a matrix and an acidic crystalline aluminosilicate zeolite ... .

(And) wherein the zeolite is ZSM-5.

(And) wherein the catalyst has become partially inactivated as a result of syngas conversion and its activity is restored.

Description and Background: This invention is concerned generally with processes for converting synthesis gas, i.e. mixtures of gaseous carbon oxides with hydrogen or hydrogen donors, to hydrocarbon mixtures and more specifically, with catalyst treatment.

Processes for the conversion of coal ... to a gaseous mixture consisting essentially of hydrogen and carbon monoxide and/or dioxide are well known.

It is also well known that synthesis gas will undergo conversion to reduction products of carbon monoxide, such as hydrocarbons, ... over a fairly wide variety of catalysts. The Fischer-Tropsch process, for example, which has been most extensively studied, produces a range of liquid hydrocarbons, a portion of which have been used as low octane gasoline. Catalysts that have been studied for this and related processes include those based on iron, cobalt, nickel, (etc.).

Recently, it has been discovered that the conversion of synthesis gas into valuable products can be greatly enhanced by employing a special type of crystalline alumino-silicate zeolite exemplified by ZSM-5 in admixture with a conventional Fischer-Tropsch catalyst.

As can well be appreciated, the patent and technical literature relating to the Fischer-Tropsch process, is, indeed, extensive and the various catalysts reported in the prior art have been used by themselves as well as in admixture with catalytically inactive supports such as kieselguhr. Although the reasons for using catalytically inactive supports have varied, nevertheless, it would appear that one reason for using the same was that it resulted in increased surface area of the Fischer-Tropsch component upon which it was deposited or admixed and that it also aided in controlling the heat requirements of the overall exothermic reactions.

It is also known in the art to admix a Fischer-Tropsch component with a material, such as silica-alumina which is known to be catalytically active for the conversion of hydrocarbons.

It is recognized that it is notoriously old in the Fischer-Tropsch art to reactivate spent catalysts by a wide variety of techniques which include not only oxidation, but also reduction.

It is to be noted however, that the novel process of this invention contains very critical steps which must be performed (as specified). Additionally, the novel process of this invention is applicable to a specific type of Fischer-Tropsch catalyst which had been prepared utilizing a water insoluble organic iron compound. For reasons which are not completely understood, it has been found that it is absolutely necessary when utilizing catalysts of this type to have the aforementioned pretreatment with syngas immediately prior to the use of these catalysts for the processing of said syngas. In other words, although one of the steps in the novel process of this invention involves treatment of the catalyst with hydrogen, it is absolutely critical that this hydrogen treatment step not be the last step prior to use of the catalyst in syngas conversion. The vast majority of prior art reactivation processes, no matter what the particular sequence, generally uses as a last step therein treatment of the catalyst with hydrogen immediately prior to its use for the conversion of syngas. Although this technique may very well be effective in treatment of iron-containing Fischer-Tropsch catalysts prepared by conventional techniques, nevertheless, it is totally inapplicable to the single particle Fischer-Tropsch catalyst prepared from water insoluble organic compounds which are utilized in the process of this invention.

The regeneration process of this invention results in the restoration of activity of the spent catalyst to an unusually high degree and enables the catalyst to be regenerated many times without any significant adverse effects.

One surprising feature of the instant catalysts is that they are unpromoted and yet they still exhibit high activity with little or no evident aging, and, in fact, are capable of converting syngas to a naphtha product while producing no more than 30 weight percent of methane plus ethane, based on total hydrocarbons."

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So, with a recyclable catalyst that sounds, to us, non-exotic and inexpensive, we can convert 70% of Coal synthesis gas into gasoline blending stock, i.e., "naphtha product"; and, the remaining 30% into Methane.

We must note, that, as in: WVU CO2 + CH4 = Hydrocarbon Syngas | Research & Development | News; for just one example, once we have such Coal-derived Methane, generated, as herein, as a byproduct of converting Coal into liquid hydrocarbons, we can react that Methane with Carbon Dioxide, recovered from whatever source, and thereby convert the both of them into even more hydrocarbons.

Again, as in "The Government of the United States of America has rights in this invention pursuant to Contract No. E(49-18)2276 awarded by the U.S. Energy Research and Development Administration"; We The People, supposedly, own at least a partial right to use this 1980 Coal liquefaction invention, in a way which might help to free us from OPEC economic bondage.

We paid for it. We own it.

Why haven't We yet, fully three decades after the fact, even been told of it?


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