WV Coal Member Meeting 2024 1240x200 1 1

Methane to Gasoline

 
Subsequent to our recent posts documenting that Methane can be generated both by the gasification of Coal and by the Sabatier conversion of Carbon Dioxide, we wanted to document that, once so obtained, Methane can also, in addition to being Tri-reformed with more CO2 into more complex and more useful hydrocarbons, be directly converted into liquid fuels - up to, and including, gasoline.
 
Enclosed are a sequence of three links, the first attached above, and three excerpts detailing the known and established processing steps that would, once we have made Methane from Coal or CO2, enable us to convert it into gasoline.
 
First, from Australia, we have:
 
"Homogeneous Conversion of Methane to Methanol. 1. Catalytic Activation and Functionalization of Methane
 
Kausala Mylvaganam, George B. Bacskay, and Noel S. Hush
[Unable to display image]School of Chemistry, University of Sydney,  Australia
J. Am. Chem. Soc., 1999, 121 (19), pp 4633–4639; Copyright © 1999 American Chemical Society 

Abstract

The recent announcement by Periana et al. (Science 1998, 280, 560) of 70% one-pass homogeneous catalysis of methane-to-methanol conversion with high selectivity in sulfuric acid solution under moderate conditions represents an important advance in the selective oxidation of alkanes, an area of considerable current interest and activity. The conversion is catalyzed by bis(2,2‘-bipyrimidine)Pt(II)Cl2. In this work, the thermodynamics of the activation and functionalization steps of the related cis-platin-catalyzed process in H2SO4 are calculated using density functional techniques, including the calculation of solvation free energies by a dielectric continuum method. It is concluded that electrophilic attack by CH4 on an intermediate which may be regarded as a tetracoordinate solvated analogue of a gas-phase, T-shaped, three-coordinate Pt(II) species, followed by oxidation of the resulting methyl complex to a methyl bisulfate ester, is thermodynamically feasible. ... While the alternative mechanism of oxidative addition does not appear to be thermodynamically feasible when using Pt(II) catalysts, catalysis by a Pt(IV) species is predicted to be, on thermodynamic grounds, a viable alternative pathway."

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So, we start out on the trail of Methane to Methanol conversion with "pathway"s that are "thermodynamically feasible" and are  "predicted to be ... viable".

Then, we have from these same Australian researchers:

 
"Homogeneous Conversion of Methane to Methanol. 2. Catalytic Activation of Methane ... the Shilov Type Reaction
 
Kausala Mylvaganam, George B. Bacskay, and Noel S. Hush
[Unable to display image]School of Chemistry, University of Sydney,  Australia
J. Am. Chem. Soc., 2000, 122 (9), pp 2041–2052; Copyright © 2000 American Chemical Society
 
Abstract

The C−H activation of methane catalyzed by cis- and trans-platin in aqueous solution has been studied by density functional based computational methods. ... The revised results provide evidence for the thermodynamic feasibility of oxidative addition of methane.".

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We were compelled to edit out a very great deal of far too technical detail in the second abstract. Suffice it to say that the "oxidative addition of methane", which yields Methanol, has had it's "thermodynamic feasibility" demonstrated. That's a good thing.

It's a "good thing" because, once the Methane, which has been synthesized from Coal or Carbon Dioxide, has been converted into the valuable liquid fuel and organic chemical manufacturing raw material, Methanol, that Methanol can be converted into gasoline, as follows:

 
We've cited Mobil, and Exxon, and even some of these same researchers, on this topic before, but repetitive emphasis is, we believe, necessary.
 
The excerpt:
 
"Aromatics, light olefins and gasoline from methanol: Mechanistic pathways with ZSM-5 zeolite catalyst

W.O. Haag, R.M. Lago and P.G. Rodewald

Mobil Research and Development Corporation, Princeton, NJ 08540


September 2001

Abstract

The conversion of methanol to hydrocarbons with zeolite ZSM-5 as catalyst provides a novel route to gasoline as well as to olefins and aromatics as chemical raw materials. The reaction is acid-catalyzed and involves alkylation of olefins and aromatics as major methanol conversion steps, accompanied by olefin isomerization, polymerization/cracking, cyclization and aromatization via hydrogen transfer. Shape-selective control of the aromatics produced results from the use of the medium pore size zeolite ZSM-5. It is shown that the true kinetic pathways are often disguised by diffusion/desorption effects. Ethylene is most likely the first olefinic hydrocarbon formed."

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So, we know from multiple, earlier-cited, sources, that we can convert both Coal and Carbon Dioxide into Methane.

As documented herein, once we have the Methane, we can convert it into Methanol. And, once we have the Methanol, we can convert it into Gasoline.