Coal and CO2 to Gasoline and Plastics via Methanol

United States Patent: 4827045

In the course of our reportage, we often make reference to ExxonMobil's Methanol-to-Gasoline, "MTG"(r), technology, usually stipulating that ExxonMobil most often posits that Methanol is to be made from Coal.

Our most recent documentation of such Methanol-to-Gasoline technology appeared in a dispatch which documented that Methanol can be synthesized from some other intriguing substances, as well, in addition to Coal, as seen in:

Pennsylvania Sunshine Converts CO2 to Methanol | Research & Development; which report included a separate link to:

"United States Patent: 4404414 - Conversion of Methanol to Gasoline; 1983; Inventors: Joe Penick, et. al., NY, PA and NJ; Assignee: Mobil Oil Corporation, New York City;   Abstract: A methanol-to-gasoline conversion process".

We wanted, in this dispatch, to further document the development of Methanol-to-Gasoline technology, since we have, over our extended course of research, come to view Methanol as a key conduit of energy, and of raw material transformation, that would enable us to make much fuller use of our abundant Coal resources; and, to begin realizing the value inherent in what has the potential to become seen as a raw material resource, to become sought after as a desired by-product of our Coal use: Carbon Dioxide.

First, we again confirm that, as seen in:

Eastman Coal to Methanol and Electric Power | Research & Development; concerning: "United States Patent Application 20060096298 - Method for Satisfying Variable Power Demand; 2006; Assignee: Eastman Chemical Company; Abstract: A process (wherein) synthesis gas streams are produced by gasification of carbonaceous materials and passed to a ... zone to produce ... methanol"; and, in:

USDOE 1976 Atmospheric CO2 to Methanol | Research & Development; which details: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Assignee: The USA as represented by the USDOE; Abstract: A method and system for synthesizing methanol from the CO2";

Methanol can be synthesized from both Coal and Carbon Dioxide.

Again, our primary intent in this dispatch is to more fully demonstrate that such Methanol, once we have it, as synthesized either from Coal or Carbon Dioxide, can then be readily transformed into Gasoline.

To that end, we present herein a sequential collection of six United States Patents issued to the same core team of Mobil Oil scientists, a team apparently headed by one key researcher.

We'll keep our excerpts brief, since additional links and comments follow, starting with the initial link in this dispatch, our series of references documenting Mobil Oil's development of a thorough understanding of how Methanol, once obtained from either Coal or Carbon Dioxide, can be efficiently transformed into Gasoline:

"United States Patent 4,827, 045 - Etherification of Methanol

Date: May, 1989

Inventors: Mohsen Harandi, et. al., NJ

Assignee: Mobil Oil Corporation, NY

Abstract: An improved process for reacting crude aqueous methanol feedstock with iso-olefinic hydrocarbons to produce C5 ... methyl tertiary-alkly ethers, which comprises: contacting the aqueous methanol feedstock with a liquid hydrocarbon extractant rich in C4 + iso-alkene under liquid extraction conditons (and) converting methanol from the aqueous raffinate phase to produce hydrocarbons.

Background: This invention relates to techniques for converting crude methanol or the like to lower methyl tertiary-alkyl ethers ... useful as octane improvers for liquid fuels, especially gasoline.

Methanol may be readily obtained from coal by gasification to synthesis gas and conversion of the synthesis gas to methanol by well-established industrial processes". And, on the very same day:

"United States Patent: 4827046 - Extraction of Crude Methanol

Date: May, 1989

Inventors: Mohsen Harandi and Hartley Owen, NJ

Assignee: Mobil Oil Corporation, NY

Abstract: An improved process for reacting crude aqueous methanol feedstock with tertiary-olefinic hydrocarbons to produce ... hydrocarbons.

Methanol may be readily obtained from coal by gasification to synthesis gas and conversion of the synthesis gas to methanol by well-established industrial processes." Then:

"United States Patent: 4831195 - Production of Ethers from Methanol

Date: May, 1989

Inventors: Mohsen Harandi and Hartley Owen, NJ

Assignee: Mobil Oil Corporation, NY

Abstract: Processes and apparatus for converting methanol or the like to intermediate olefins and etherification products... .

Methanol may be readily obtained from coal by gasification to synthesis gas and conversion of the synthesis gas to methanol by well-established industrial processes." And, later:

United States Patent: 4981491 - Production of Ether-Rich Fuel

Date: January, 1991

Inventors: Mohsen Harandi and Hartley Owen, NJ

Assignee: Mobil Oil Corporation, NY

Abstract: Methanol or other alcohol is converted to high octane gasoline components ... .

This invention relates to techniques for converting crude methanol or other ... alcohols to ... gasoline range hydrocarbons.

This invention relates to techniques for converting crude methanol or other ... alcohols to gasoline range hydrocarbons. In particular, this invention relates to an improvement in utilizing methanol-to-gasoline (MTG) processes and operating synfuel systems ... . Methanol is considered the most important oxygenate feedstock because of its widespread availability and low cost." Then:

United States Patent: 5009859 - Extraction and Reactor System

Date: April, 1991

Inventors: Mohsen Harandi and Hartley Owen, NJ

Assignee: Mobil Oil Corporation, VA

Abstract: An improved extraction and reactor system for reacting crude aqueous alcohol feedstock ... to produce tertiary-alkyl ethers. This system is useful in extracting crude methanol in MTBE production.

(And) catalytic reactor means for converting methanol ... to produce hydrocarbons.

Methanol may be readily obtained from coal by gasification to synthesis gas and conversion of the synthesis gas to methanol by well-established industrial processes." And, finally:

United States Patent: 5026529 - Production of Ethers from Methanol

Date: June, 1991

Inventors: Mohsen Harandi and Hartley Owen, NJ

Assignee: Mobil Oil Corporation, NY

Abstract: Improved operating techniques and apparatus for converting methanol or the like to intermediate olefins and etherification products ... .

A continuous catalytic reactor system for converting crude methanol to ... ethers.

This invention also provides a unique reactor and recovery system for converting methanol to lower olefins.

In view of the availability and low cost of synthetic methanol (MeOH), primary emphasis is placed on this feedstock material ... .

In its broader aspects, this invention relates to an integrated system for converting crude methanol to valuable products ... (such as) liquid fuels, especially gasoline.

Methanol may be readily obtained from coal by gasification to synthesis gas and conversion of the synthesis gas to methanol by well-established industrial processes."

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We'll close our citations of Mobil Oil there, with some apologies for the, perhaps, tedious nature of the presentation.

However, it could have been worse. Harandi and his Mobil Oil collaborators in the development of the "MTG"(r) technological base were prolific.

And, we wanted to save some space to document, as well, that, not only can Methanol be so thoroughly converted into Gasoline, it can also serve as the raw material from which we can synthesize a number of industrially-valuable plastics, as seen in:

Honeywell’s UOP and Total Petrochemicals Successfully Demonstrate Technology to Produce Plastics from Feedstocks Other Than Oil; which informs that:

"UOP LLC, a Honeywell (NYSE: HON) company, announced today that Total Petrochemicals has successfully demonstrated UOP technology that will enable the use of feedstocks other than petroleum to produce plastics and other petrochemicals.A demonstration unit built by Total Petrochemicals at its complex in Feluy, Belgium, used UOP/Hydro MTO methanol-to-olefins technology to convert methanol to ethylene and propylene. The propylene was then successfully converted to polypropylene product. This demonstration proves that propylene produced from methanol at a semi-commercial scale is suitable for plastics production.

Methanol is commonly produced from ... coal."

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We have, by the way, cited France's "Total" company previously, as in, for one instance, our report:

France, China, CoalTL & CO2 Recycling | Research & Development; which documented the "latest developments in China (concerning) the production of coal-to-liquids, coal-to-dimethyl ether, coal-to-olefins and coal to SNG (i.e., "synthetic natural gas"). The Chinese coal chemical industry is backed by intense government interest, with new generation technology from Western multinationals (including) Total Petrochemicals, Celanese, and Dow Chemical ... . "

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So valuable a raw material is Methanol, and so obtainable is it from some of our abundant resources such as Coal, that some noted scholars, including our oft-cited University of Southern California Carbon-conversion genius, Nobel laureate George Olah, and his USC colleague Surya Prakash, have called for the establishment of a fuel and manufacturing industry based on Methanol.

More on that can be learned via:

Methanol economy - Wikipedia, the free encyclopedia; wherein we're told, among many things, that:

"The methanol economy is a suggested future economy in which methanol replaces fossil fuels as a means of energy storage, fuel and raw material for synthetic hydrocarbons and their products.

Since the 1990s Noble prize winner George Olah started to advocate the methanol economy and in 2006 he and two co-authors (G.K. Surya Prakash and Alain Goeppert) published a book around this theme. In these publications, they summarize the state of our fossil fuel and alternative energy sources, their availability and limitations before suggesting a new approach in the so called methanol economy.

Methanol is a fuel for heat engines and fuel cells. Due to its high octane rating it can be used directly as a fuel ... using existing internal combustion engines.

Methanol is a liquid under normal conditions, allowing it to be stored, transported and dispensed easily, much like gasoline and diesel fuel is currently.

It can also be readily transformed ... into dimethyl ether, a diesel fuel substitute ... .

Methanol is already used today on a large scale ... as a raw material to produce numerous chemical products and materials. In addition, it can be readily converted in the methanol to olefin (MTO) process into ethylene and propylene, which can be used to produce synthetic hydrocarbons and their products ... .

Methanol can be efficiently produced from a wide variety of sources including still abundant fossil fuels (such as) coal, (and, from) agricultural products and municipal waste, wood and varied biomass.

More importantly, it can also be made from chemical recycling of carbon dioxide.

Initially the major source will be the CO2 rich flue gases of fossil fuel burning power plants or exhaust of cement and other factories. (And) even the low concentration of atmospheric CO2 itself could be captured and recycled via methanol, thus supplementing nature’s own photosynthetic cycle.

Efficient new absorbents to capture atmospheric CO2 are being developed, mimicking plant life’s ability. Chemical recycling of CO2 to new fuels and materials could thus become feasible, making them renewable on the human timescale.

In an economy based on methanol, methanol could be used as a fuel ... (in) internal combustion engines.

Methanol has a high octane rating ... which makes it a suitable gasoline substitute. It has a higher flame speed than gasoline, leading to higher efficiency as well as a higher latent heat of vaporization (3.7 times higher than gasoline), meaning that the heat generated by the engine can be removed more effectively, making it possible to use air cooled engines. Besides this methanol burns cleaner than gasoline and is safer in the case of a fire.

Methanol itself is not a good substitute for diesel. Methanol can, however, be converted by dehydration to dimethyl ether (DME), which is a good diesel fuel with a cetane number of 55-60 as compared to 45-55 for regular diesel fuel (and) which excels its cold start ability in winters and reduces its noise. Compared to diesel fuel, DME has much lower emissions of NOx and CO and does not emit any particulate matter ... .

Methanol can also be used, and is in fact already used in the production of) biodiesel ... .

DME can also be blended with LPG and used as a cooking or heating fuel as is already the case in China.

Methanol is already used today on a large scale as raw material to produce a variety of chemicals and products.

Through the methanol to gasoline (MTG) process, it can be transformed into gasoline.

Using the methanol to olefin (MTO) process, methanol can also be converted to ethylene and propylene, the two largest chemicals produced by the petrochemical industry.

These are important building blocks for the production of essential polymers (LDPE, HDPE, PP) and other chemical intermediates (that) are currently produced mainly from petroleum feedstock.

Their production from methanol could therefore reduce our dependency on petroleum.

The methanol needed in the methanol economy can not only be synthesized from a wide array of carbon sources including still available fossil fuels and biomass but also CO2 emitted from fossil fuel burning power plants and other industries and eventually even the CO2 contained in the air.

(Importantly), methanol can ... be produced from CO2 by catalytic hydrogenation of CO2 with H2 where the hydrogen has been obtained from water electrolysis.

Methanol may also be produced through CO2 electrochemical reduction, if electrical power is available.

The energy needed for these reactions in order to be carbon neutral would come from renewable energy sources such as wind, hydroelectricity and solar ... .

In effect, all of them allow free energy to be stored in easily transportable methanol, which is made immediately from hydrogen and carbon dioxide, rather than attempting to store energy in free hydrogen.

The necessary CO2 would be captured from fossil fuel burning power plants and other industrial flue gases including cement factories. (Even) the CO2 content in the air could also be used.

Methanol economy advantages compared to a hydrogen economy:

Efficient energy storage by volume, as compared with compressed hydrogen.And when hydrogen pressure-confinement vessel is taken into account, an advantage in energy storage by weight can also be realized.

The volumetric energy density of methanol is considerably higher than liquid hydrogen ... .Hence there is actually more hydrogen in a liter of methanol ... than in a liter of liquid hydrogen ... .

A liquid hydrogen infrastructure would be prohibitively expensive.

Methanol can use existing gasoline infrastructure with only limited modifications.

Can be made from any organic material using proven technology going through syngas. There is no need to use food crops and compete with food production.

Methanol obtained from fossil fuels has a lower price than ethanol.

Can be blended in gasoline like ethanol."

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And, even though the nearly-omniscient Wikipedia doesn't much dwell on the fact, we call your attention to the fact that they do confess:

"Methanol can ... be converted ... to dimethyl ether (DME), which is a good diesel fuel" and, via "the methanol to gasoline (MTG) process, it can be transformed into gasoline".

Finally, to confirm it yet again, as seen, for some additional examples, in:

California Converts Power Plant CO2 to Methanol | Research & Development; concerning: "US Patent Application 20060235091 - Efficient and Selective Conversion of Carbon Dioxide to Methanol; 2006; Inventors: George Olah and Surya Prakash, CA; Abstract: An environmentally beneficial method of producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning powerplants, industrial exhaust gases or the atmosphere itself"; and, in:

US Navy Coal + H2O = Low Cost Methanol | Research & Development; which reports: "United States :Patent 4,476,249 - Low Cost Method for Producing Methanol; 1984; Assignee: The Johns Hopkins University, Baltimore; The Government has rights in this invention pursuant to Contract N00024-78-C5384 awarded by the Department of the Navy; Abstract: Method for producing low cost methanol ... from coal";

we can make such a valuable, nearly-precious liquid fuel; gasoline and diesel precursor; and, plastics manufacturing raw material, i.e., Methanol, from both our unwanted Carbon Dioxide and our abundant Coal.