Conoco 1985 Coal to Gasoline & Methanol

A few years ago now, in the midst of the long course of our reportage documenting the plain fact, that, our abundant domestic Coal can, cleanly and efficiently, be converted into anything we now allow our nation's economy and our US citizens' personal prosperities to be sacrificed on the altars of OPEC and Big Oil for the supply of, we likened the fact that Coal can, plainly and now irrefutably, be profitably converted into Gasoline, to an elephant squatting in the middle of our living room floor.
It's there, and no genuinely honest or sane person can deny that it's there. But, apparently, no one, not even anyone in US Coal Country, wants to openly admit that it's there and then have to feel compelled to get off their cans, get up and out of their cushy chairs, and do something about it.
Maybe it's just too big a job for them, and they feel intimidated by it; and, by everyone who, feigning wisdom and indeed sounding wise, says that it can't be done.
And, everyone thus, now almost awkwardly, and ridiculosuly, pretends that it's not there.
No one talks about it publicly, no one remarks on it openly; and, we all just seem to adjust our chairs so that we can look around it to get a better view of the television, where now-robotic news people are reporting on stuff we really want to hear about and be lazily entertained by, like US military actions in the oil-rich Middle East and things that are going up, like gasoline prices and Coal Country unemployment.
Maybe that'll change some day; we hope so. But, until then, we'll keep shoveling that elephant's turds into your laps; trying to tear everyone's attention away from the talking heads on the boob tube so that we can all start shoveling, instead, a little more Coal.
Toward that end, if you recall, we earlier reported on how that titan of the oil industry, Conoco, had developed some intriguing technologies for the conversion of Coal into hydrocarbon synthesis gas; and, for the catalytic condensation of that synthesis gas into liquid fuels.
One straightforward example can be accessed via:

"United States Patent 4,218,389 - Process for Making Methanol; 1980; Assignee: Conoco, Inc.; A process for producing methanol from air-blown gasified coal."

And, Conoco later, quite recently, developed a, to us, very intriguing way of gasifying Coal, so that nifty stuff like Methanol could be made from it, as seen in our report of:

West Virginia Coal Association | Conoco 2011 Coal + CO2 + H2O + O2 = Syngas | Research & Development; concerning:

"United States Patent 7,959,829 - Gasification System and Process; 2011; Assignee: ConocoPhillips Company; A system and process for gasifying carbonaceous feedstock ... in two separate reactor sections, thereby producing mixture products comprising synthesis gas. A process for gasification of a carbonaceous material (which includes) pyrolysing ... a first slurry stream comprising a slurry of particulate carbonaceous material in a liquid carrier (and) wherein said particulate carbonaceous material is ... coal (and) wherein said carrier liquid is ... Carbon Dioxide".

In any case, Methanol, as can be made from Coal, via, for just one out of many examples, the above-cited Conoco process of "United States Patent 4,218,389 - Process for Making Methanol", is, as we said, some pretty nifty stuff to have.

We can, as explained succinctly in one, out of several similar, of our reports:

ExxonMobil "Coal to Clean Gasoline" | Research & Development; concerning the information piece: "Coal to Clean Gasoline; Xinjin Zhao, Ron D. McGihon and Samuel A. Tabak; ExxonMobil Research and Engineering Company, USA, discuss ExxonMobil's methanol to gasoline technology for the production of clean gasoline from coal"; convert that Coal-derived Methanol rather directly into Gasoline.
However, Methanol, in and of itself, is a valuable raw material that can be utilized in the production of other needed things, as well, as explained by:
Methanol - Wikipedia, the free encyclopedia; wherein we're told, in part, that: "(the) main applications for methanol are the production of formaldehyde (used in construction and wooden boarding), acetic acid (basis for PET-bottles), ... and more recently for the formation of methy esters in the production of bio-diesel. In China, demand is expected to grow exponentially, not only caused by a growing internal market of the traditional applications, but accelerated by new applications, such as direct blending (with gasoline), Methanol-To-Olefins (e.g. propylene) and DME. Methanol can also be used to produce gasoline".
It's important to note, however, that Methanol is toxic, and can be dangerously, even irresponsibly, misused.
As seen, for one example, in:
http://www.methanol.org/Environment/Resources/Environment/Methanol-Fracking-Fluid-White-Paper-Aug-2011.aspx; "White Paper: Methanol Use in Hydraulic Fracturing Fluids; Prepared for Methanol Institute;
Leakage of Methanol as Part of Fracking Fluids through a Natural Gas Well Casing, With Methanol Reaching a Residential Water Well".
But, Gasoline ain't exactly Rocky Mountain Spring Water, either, and we still want and need it.
Herein, as excerpted from the initial link in this dispatch, Conoco explains how we can get both, Methanol and Gasoline, or, more exactly, Methanol and some hydrocarbons useful in the blending of Gasoline, in one contiguous process, from Coal:
"United States Patent 4,534,772 - Process of Ether Synthesis
Date: August, 1985
Inventor: Eric Reichl, CT
Assignee: Conoco Inc., DE
Abstract: A method for producing fuel comprised of gasoline rich in methanol and methyl ethers derived from coal, which process comprises gasifying the coal to produce carbon monoxide and hydrogen, steam shifting the gasification product to produce additional hydrogen, cleaning up the shifted product, catalytically converting the cleaned shifted gas to a mixture of alcohols, separating a methanol fraction from the mixture of alcohols, dehydrating the remaining alcohols to olefins, etherifying the olefin mixture with a portion of the removed methanol fraction, and blending into gasoline the resulting ether mixture and a second portion of the removed methanol fraction.
Claims: A process for producing a high octane liquid gasoline fuel product mixture rich in methanol and methyl ethers from coal consisting of the sequence of steps as follows: 

(a) gasifying coal to form a coal gasification product gas mixture comprising hydrogen and carbon monoxide, 
(b) contacting said coal gasification product gas with water and a shift conversion catalyst to catalytically react said water with said carbon monoxide of said gasification product gas to form a shift product gas mixture comprising carbon dioxide and hydrogen, 

(c) subjecting said shift product gas mixture to a clean-up step to produce a cleaned shift product gas mixture, 

(d) contacting said cleaned shift product gas mixture with an alcohol synthesis catalyst to form a synthesis product mixture of alcohols, said synthesis product mixture of alcohols comprising methanol, and said alcohol synthesis catalyst comprising alkali modified zinc oxide and chromium oxide, 

(e) separating said synthesis product mixture of alcohols into a methyl alcohol separation product mixture and a higher alcohol separation product mixture, said methyl alcohol separation product mixture comprising a substantially larger proportion of methanol than said synthesis product mixture of alcohols, and said higher alcohol separation product mixture further comprising substantially all of the alcohols other than methanol from said synthesis product mixture of alcohols, 

(f) dehydrating said higher alcohol separation product mixture with a catalyst to form a dehydration product mixture and water, said dehydration product mixture comprising olefins, and said catalyst comprising alumina, 

(g) catalytically reacting said olefins of said dehydration product mixture with a portion of said methyl alcohol separation product mixture in the presence of an ether synthesis catalyst at about 125 F and 300 psi to form a methyl ether product mixture, said ether synthesis catalyst comprising acidic ion exchange resin, 

(h) mixing the remainder of said methyl alcohol separation product with said methyl ether product mixture to form a methyl alcohol and methyl ether product mixture as substantially the only liquid product of said coal gasified in step (a), and 

(i) mixing gasoline with said methyl alcohol and methyl ether product mixture to form a high octane fuel product, 

whereby substantially all of the alcohols formed in step (d) are formed into a mixture of methyl alcohol and methyl ethers and are mixed with gasoline to produce a high octane liquid gasoline fuel product rich in methyl alcohol and methyl ethers.
(Note, that, further above, it is specified to contact the "coal gasification product gas with water and a shift conversion catalyst to catalytically react said water with said carbon monoxide of said gasification product gas to form a shift product gas mixture comprising carbon dioxide and hydrogen", so that more Hydrogen can be formed to enable the formulation of a synthesis gas with the appropriate Carbon Monoxide to Hydrogen ratio for efficient catalytic hydrocarbon synthesis. The Carbon Dioxide byproduct could, of course, be collected and directed back into the initial Coal gasification, as via the above-cited Conoco process of
"United States Patent 7,959,829 - Gasification System", where it would be consumed in the generation, from Coal primarily, of more hydrocarbon synthesis gas. However, as Conoco themselves admit, as, for one example, in our report of:

"United States Patent 6,664,207 - Catalyst for Converting Carbon Dioxide to Oxygenates; 2003; Assignee: ConocoPhillips Company; Abstract: A catalyst and process for converting carbon dioxide into oxygenates. A catalyst composition for converting carbon dioxide to methanol and dimethyl ether";

they now have catalysts in hand that would enable the conversion of the Carbon Dioxide, too, along with the Carbon Monoxide, in combination with the Hydrogen, into Methanol. - JtM)

Summary: The process of the present invention beneficially provides an improved and simplified process for the production of ethers suitable for use in blending high octane gasoline from coal."

-------------------------

Our excerpts don't fully represent the details, of course; and, we want to emphasize that, in addition to Methanol, only some hydrocarbon components of Gasoline blending stock, not a fully-formulated Gasoline, are being synthesized herein from Coal.

Still, since, as explained for another example in:

"United States Patent 6,638,892 - Syngas Conversion and Catalyst Employed Therefor; 2003; Assignee: ConocoPhillips Company; Abstract: A process for the conversion of syngas by contact of syngas under conversion conditions with catalyst having as components zinc oxide, copper oxide, aluminum oxide, ... zeolite and clay in ... a one step process for conversion of syngas to dimethyl ether (and) a two step process for conversion of syngas to light olefins ... . Dimethyl ether is a clean and efficient alternative diesel fuel which can be produced by the dehydration of methanol which can be synthesized from syngas. Syngas is obtained using well known processes by the partial combustion or gasification of any organic material such as coal";

a simple catalyst addition could enable a contiguous process that converts the Coal syngas, through Methanol, and the subsequent "dehydration of methanol", into an "efficient alternative diesel fuel".

Further, as seen in:

"United States Patent 4,825,013 - Higher Alcohols from Lower Carbon Number Alcohols; 1989; Assignee: The Dow Chemical Company; Abstract: A process for forming an alcohol fraction boiling in the range of motor gasoline that is enriched in higher alcohols, comprises contacting a mixture of hydrogen, carbon monoxide and a lower alkanol with a (specified and detailed catalyst) ... under conditions sufficient to convert at least some of the one or more lower alcohols to higher alcohols. A process comprising contacting a mixture of hydrogen, carbon monoxide and one or more lower alcohols with a heterogeneous catalyst ... under conditions sufficient to convert at least some of the one or more lower alcohols to higher alcohols (and) wherein the one or more lower alcohols contain methanol. The hydrogen and carbon monoxide required for this process may be obtained by ... the ... gasification of hydrocarbonaceous materials such as coal";

we could, in fact, react Coal-derived Methanol, as synthesized via the process of our subject, "US Patent 4,534,772 - Process of Ether Synthesis", with even more "hydrogen and carbon monoxide ...  obtained by ... the ... gasification of ... coal", and thereby make outright "higher alcohols ... boiling in the range of motor gasoline".

To which "motor gasoline", we conjecture, we could add, as specified by Conoco, and as verified by our US Government experts, in "US Patent 4,534,772", the co-product "additional ethers suitable for use in blending high octane gasoline" which were themselves made "from coal".