WV Coal Member Meeting 2024 1240x200 1 1

Conoco Hydrogenates More Carbon Monoxide

United States Patent: 6730708

Nowhere in the extended Disclosure of the ConocoPhillips US Patent we report in this dispatch is the dirty, four-letter word "Coal", even in passing, mentioned.

 

But, that's okay.

 

It is, in fact, the Disclosure of an improvement on the processing of Synthesis Gas, "Syngas", a blend of Carbon Monoxide and Hydrogen, to produce, preferentially, Hydrocarbons; no matter what the source of that Syngas might be.

And, it is closely related to another Conoco technology we recently reported, as in our dispatch concerning:

 

"United States Patent: 6727289 - Boron Promoted Catalysts and Fischer-Tropsch Processes; Assignee: ConocoPhillips Company, TX; Abstract: A process is disclosed for producing hydrocarbons. The process involves contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst (which) includes at least a Fischer-Tropsch metal and boron."

 

All of that has some implications we point out and emphasize, following excerpts from:

 

"US Patent 6,730, 708 - Fischer-Tropsch Processes and Catalysts Using Aluminum Borate

 

Date: May, 2004

 

Inventor: Ajoy Raje, et. al., OK

 

Assignee: ConocoPhillips Company, TX

 

Abstract: A process is disclosed for the hydrogenation of carbon monoxide. The process involves contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst system in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream, preferably comprising hydrocarbons. In accordance with this invention the catalyst system used in the process includes at least one catalytic material for Fischer-Tropsch reactions (e.g., iron, cobalt, nickel and/or ruthenium), preferably comprising cobalt, and a support comprising aluminum borate.

 

Claims: A process for the production of hydrocarbons, comprising: contacting a feed stream comprising hydrogen and carbon monoxide with a cobalt-containing catalyst system in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream comprising hydrocarbons ... .

 

(And) wherein the support comprises between about 0.5 and about 5 wt % boron.

(And) wherein said support comprises aluminum in an amount between about 20 and about 60 wt % of the support, and boron in an amount sufficient to cause the surface of the support to be more acidic than the surface of a neutral (pH=7) alumina but less acidic than a zeolite cracking catalyst.

 

A process for the production of hydrocarbons, comprising: contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst system in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream comprising hydrocarbons ... .

 

Field: The present invention relates to a process for the hydrogenation of carbon monoxide to produce hydrocarbons ... . More particularly, the present invention relates to the use of an aluminum borate supported Fischer-Tropsch catalyst. Still more particularly, the present invention relates to the use of a cobalt or a promoted cobalt Fischer-Tropsch catalyst on an aluminum borate support.

 

Background: (The) preparation of hydrocarbons from syngas, is well known in the art and is usually referred to as Fischer-Tropsch synthesis, the Fischer-Tropsch process, or Fischer-Tropsch reaction(s). The Fischer-Tropsch reaction involves the catalytic hydrogenation of carbon monoxide to produce a variety of products ranging from methane to higher aliphatic hydrocarbons and/or alcohols.

 

The methanation reaction was first described in the early 1900's, and the later work by Fischer and Tropsch dealing with higher hydrocarbon synthesis was described in the 1920's.

The Fischer-Tropsch synthesis reactions are highly exothermic and reaction vessels must be designed for adequate heat exchange capacity. Because the feed streams to Fischer-Tropsch reaction vessels are gases, while the product streams include liquids, the reaction vessels must have the ability to continuously produce and remove the desired range of liquid hydrocarbon products.

 

The first major commercial use of the Fischer-Tropsch process was in Germany during the 1930's. More than 10,000 B/D (barrels per day) of products were manufactured with a cobalt based catalyst in a fixed-bed reactor.

 

(The synthesis gas used in that German facility was generated from Coal.)

 

Catalysts for use in the Fischer-Tropsch synthesis usually contain a catalytically active metal of Group VIII. In particular, iron, cobalt, nickel, and ruthenium have been used as the catalytically active materials. Nickel is useful for a process in which methane is a desired product. Iron has the advantage of being readily available. Ruthenium has the advantage of high activity and thus is typically used a promoter for another of the catalytic materials, due to the limited availability of ruthenium.

 

Cobalt has ... been investigated as a catalyst for the production of hydrocarbons with weights corresponding to the range of the gasoline, diesel, and higher weight fractions of crude oil.

Additionally, the catalysts often contain one or more promoters and a support or carrier material. Research is continuing on the development of more efficient Fischer-Tropsch catalyst systems and catalyst systems that increase the activity of the catalyst. In particular, catalyst supports that have been investigated include ceramic supports. Ceramic supports include various structural forms of alumina, such as alpha and gamma alumina, in addition to silica, titania, zirconia, zeolites, spinels, sol-gels, co-gels, and the like. It is known that the catalyst activity can vary with the composition and structure of the support.

Despite the vast amount of research effort in this field, Fischer-Tropsch catalysts supported on current ceramic supports are not always sufficiently active. Hence, there is still a great need to identify new catalyst supports, particularly catalyst supports that result in improved catalyst activity and thus enhance the process economics.

 

Summary: This invention relates to a process and catalyst for producing hydrocarbons, and includes a catalytically active material containing cobalt and a catalyst support containing aluminum borate. The Fischer-Tropsch synthesis process includes contacting a feed stream comprising hydrogen and carbon monoxide with this supported catalytic material in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream including hydrocarbons.

 

The feed gases charged to the synthesis process comprise hydrogen, or a hydrogen source, and carbon monoxide. H2 /CO mixtures suitable as a feedstock for conversion to hydrocarbons according to the synthesis process can be obtained from ... processes known in the art.

 

Preferably, the hydrogen is provided by free hydrogen, although some Fischer-Tropsch catalysts have sufficient water gas shift activity to convert some water to hydrogen for use in the Fischer-Tropsch process."

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Note, yet again, that, although free Hydrogen might be preferable, it isn't absolutely required. All that's really needed, to synthesize hydrocarbons, is Carbon Monoxide and Water.

 

And, we have to beat it to death:

 

We can manufacture all of the Carbon Monoxide we might ever want by simply blowing Carbon Dioxide through red-hot Coal. As witnessed, for example, by:

 

"United States Patent: 4564513 - Process for the Production of Carbon Monoxide

 

Date: January, 1986

 

Inventor: Dieter Bechler, et. al., Germany

 

Assignee: Bayer AG

 

Abstract: Carbon monoxide is produced in an improved process in a carbon-filled, water-cooled generator in the configuration of a truncated cone in the longitudinal section, by the gasification of said carbon with a mixed gas of oxygen and carbon dioxide ... (and) wherein the carbon is in the form of coke."

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You don't suppose that anyone in the Ohio Valley remembers how to make a little "coke", do you?

 

If so, there should be some Carbon Dioxide available somewhere - maybe from one of the Natural Gas stripping and cleaning operations that might be soon popping up in the area.

 

And, we should, thus, be able to make some Carbon Monoxide, and, through the Conoco processes of

United States Patent: 6730708 and United States Patent: 6727289, start using that Carbon Monoxide, made from Carbon Dioxide and hot Coal, to make, as according to Conoco, some "hydrocarbons with weights corresponding to the range of the gasoline, diesel, and higher weight fractions of crude oil", or, even, again according herein to Conoco, a wider "variety of products ranging from methane to higher aliphatic hydrocarbons and/or alcohols".

 

Finally, according to Conoco: "some Fischer-Tropsch catalysts have sufficient water gas shift activity to convert some water to hydrogen for use in the Fischer-Tropsch process"; so, strictly speaking, we don't really have to go to the expense of making free Hydrogen "for use in the Fischer-Tropsch process" that hydrogenates and converts Carbon Monoxide into such a full range of "hydrocarbons and/or alcohols".

 

Should the doubters among us demand it, however, we remind you, that, as we reported in:

 

Solar-Powered Hydrogen Generation | Research & Development; concerning: "United States Patent 7,726,127 - Solar Power for Thermochemical Production of Hydrogen";

 

options exist which would enable us to harness freely-available environmental energy to make any of the Hydrogen which might be required out of plain old Water.