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Pennsylvania Sunshine Converts CO2 to Methanol

United States Patent: 5720858

Relative to our headline on this dispatch, as we will see, once Pennsylvania uses Solar energy to convert the Carbon Dioxide to Methanol, Mobil Oil knows how to convert that Methanol to Gasoline.

And, there is even more to it.

First, we remind you of: Penn State Solar CO2 + H2O = Methane | Research & Development | News; in which we're told of the: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; 2009; The Pennsylvania State University"; and, the outline of a method for the "solar conversion of carbon dioxide and water vapor to methane".

 

 

Following, as excerpted from the initial link in this dispatch, we see that, once we have the Methane, as in the Penn State report noted above, synthesized from H2O and Carbon Dioxide, in a process driven by Solar energy, Pittsburgh says that we can use Solar energy again, to further convert that CO2-derived Methane into Methanol.

Comments, with additional links, are inserted within, and appended to, our excerpts from:

"United States Patent 5,720,858 - Method for the Photocatalytic Conversion of Methane

Date: February, 1998

Inventors: Richard Noceti, et. al., Pittsburgh, PA

(Note: The named inventors' specific affiliations are not clearly identified in the USPTO file of this Patent. However, we refer you to an earlier dispatch, which should serve to clear that issue up; and, to put another spin on it all, as in: Pittsburgh DOE Converts Methane to Gasoline | Research & Development; which concerns the: "Conversion of Methane to Gasoline-Range Hydrocarbons; Charles E. Taylor and Richard P. Noceti; U.S. Department of Energy; Pittsburgh Energy Technology Center; Pittsburgh, PA;  Abstract: Existing processes have been assembled in a novel combination capable of producing higher hydrocarbons from methane with high yield and selectivity". Noceti, as other documents attest, later became a Supervisory Physical Scientist in the Chemistry and Surface Science Division of the USDOE's National Energy Technology Laboratory, in Philadelphia, PA.)

Assignee: The United States of America

Abstract: A method for converting methane to methanol is provided comprising subjecting the methane to visible light in the presence of a catalyst and an electron transfer agent. Another embodiment of the invention provides for a method for reacting methane and water to produce methanol and hydrogen comprising preparing a fluid containing methane, an electron transfer agent and a photolysis catalyst, and subjecting said fluid to visible light for an effective period of time.

The United States Government has rights to this invention pursuant to employee/employer relationship of the inventors to the U.S. Department of Energy at the Pittsburgh Energy Technology Center.

Claims: A method for converting methane to methanol comprising subjecting a mixture of methane and water to visible light in contact with a transition metal oxide catalyst and an electron transfer agent.

(And) wherein the methane is pretreated ... by saturating the methane with water.

(And) wherein the water contains hydrogen peroxide.

(And) wherein the conversion occurs at a temperature of at least approximately 70C.

(And) wherein the visible light has a wavelength of at least approximately 400 nm.

(Visible light with a 400 nanometer wavelength would, various web-based references indicate, be on the "border" between "near-ultraviolet" and blue on the spectrum.)

(And) wherein the conversion occurs at a pressure selected from a range of between approximately 0.03 atmospheres and 500 atmospheres.

(So, we can convert Methane and Water, with a little Hydrogen Peroxide added, which is no big deal, the local Thrift(r) Drug Store should have some on the shelves, to Methanol, at a temperature less than the boiling point of Water, in a reaction that takes place at virtually any pressure, even, at "0.03 atmospheres", a semi-vacuum, and, under exposure to a light source that we might not even need sunglasses, much less welder's goggles, to look at.)

The method ... wherein the catalyst contains a dopant selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, lanthanum, lithium, silver, platinum and combinations thereof.

(And) wherein the transition metal is selected from the group consisting of tungsten, bismuth, ruthenium, iron, cadmium, and combinations thereof. 

A method for reacting methane and water to produce methanol and hydrogen ... wherein the electron transfer agent is selected from ... methyl viologen dichloride hydrate, 1,4-dicyanobenzene, p-dicyanobenzene, chloranil ... .

(Most of the "electron transfer" agents they name are known and commercially available chemical reagents. However, they can be expensive. The "methyl viologen dichloride hydrate", for instance, could cost up to forty bucks a gram. And, for you staunch patriots, or obstinate fossils, out there who have resisted the imposed transition to metrics, there are about 28 grams in an ounce. Conversely, "chloranil" is a plant-based product, and suppliers in India will send us all we need for two or three bucks a pound. That still sounds like a lot, but, the reagents are, like chlorophyll in green plants, only serving a sort of catalytic function in the process; and, our read of it is that they are not actually involved with, or consumed in and used up by, the chemical reactions. Thus, a little might go a long way, and the expense might not be too great.)

The method ... wherein said oxide of a transition metal contains a dopant selected from the group consisting of platinum, lanthanum, copper, and combinations thereof.

A method for converting methane to methanol comprising: saturating methane with water; heating the saturated methane to at least approximately 70 C.; mixing the heated, saturated methane with water and effective amounts of a transition metal oxide catalyst and an electron transfer agent to create a reaction fluid; and, exposing the reaction fluid to visible light.

(And) wherein the catalyst is tungsten trioxide and the electron transfer agent is methyl viologen dichloride hydrate.

(And) wherein the reaction fluid is exposed to the visible light for ... approximately 1 second (to) 5 minutes.

Background and Field: The present invention relates to a method for converting methane into methanol, and more particularly, the present invention relates to a method for converting methane and water to methanol and hydrogen using visible light and a catalyst.

The importance of methanol as a feedstock chemical and as a fuel is undeniable. Methanol can be derived from methane."

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Let's end there and cut to the chase:

As in our above-cited earlier dispatch, concerning: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels", from Penn State University, we know how to convert Carbon Dioxide into Methane, using sunlight to drive the process.

As in our subject: "United States Patent 5,720,858 - Method for the Photocatalytic Conversion of Methane", we know how to convert that CO2-derived Methane into Methanol, again using, essentially, a portion of sunlight to drive the process.

And, via a reference we haven't previously and directly cited in our earlier reports, though we have referenced, and, as in: Mobil Oil Coal to Methanol to Gasoline | Research & Development; documented variations of the technology many times, herein, following, is further confirmation of the fact, that, once we have the Methanol, as herein made in Pennsylvania by using Sunlight to, first, convert Carbon Dioxide into Methane; and, then, after again using, essentially, Sunlight to convert that CO2-derived Methane in Methanol, we can then convert that Methanol directly into Gasoline, as in:

"United States Patent: 4404414 - Conversion of Methanol to Gasoline Date: September, 1983

Inventors: Joe Penick, et. al., NY, PA and NJ

Assignee: Mobil Oil Corporation, New York City

Abstract: A methanol-to-gasoline conversion process in which the conversion is conducted in a number of reactors which are fed directly by the charge, preferably in equal proportions. A diluent gas, preferably recycled light hydrocarbons separated from the product, is passed in sequence through each of the beds to carry away the heat of reaction. In this way, a high effective recycle ratio is maintained in each bed although the actual recycle ratio for the entire system is low.

Claims: A process for the conversion of an oxygenated organic compound to a gasoline boiling range hydrocarbon product, which comprises: charging a portion of the oxygenated organic compound to each of a plurality of reaction zones containing a ZSM-5 type conversion catalyst in primary and secondary stages of a multi-stage reactor system ... .

A process ... in which the oxygenated organic compound charged to each reaction zone is substantially completely converted to hydrocarbon product within the reaction zone to which it is charged.

A process ... in which the methanol is dehydrated over a ... catalyst in a dehydration reactor and subsequently charged to at least one reaction zone for further conversion to hydrocarbon product. 

A process ... in which the dehydration products are converted to hydrocarbons over a crystalline aluminosilicate zeolite catalyst (and) in which the zeolite is ZSM-5.

Background and Field: This invention relates to a process for converting methanol and other oxygenated organic compounds to hydrocarbons, especially to gasoline boiling range products.

Processes for converting lower alcohols such as methanol to hydrocarbons are known and have become of great interest in recent times because they offer an attractive way of producing liquid hydrocarbon fuels, especially gasoline, from sources which are not of liquid petroliferous origin. In particular, they provide a way by which methanol can be converted to gasoline boiling range products in good yields. The methanol, in turn, may be readily obtained from coal ... ".

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So, according Mobil Oil, as immediately above, and as confirmed by our US Government, we can, through Methanol, which can "be readily obtained from coal", synthesize Gasoline from Coal.

Perhaps as importantly:

Via the combination of Penn State University's published "High-Rate Solar Photocatalytic Conversion of CO2" process, which uses environmental energy to synthesize Methane from Carbon Dioxide; and, the technique of our own US Government's "United States Patent 5,720,858", which uses environmental energy to convert that Methane into Methanol; followed by Mobil Oil's technology of "United States Patent 4,404,414"; which converts that Methanol - - while acknowledging that such Methanol can also "be readily obtained from coal" - - into Gasoline;we can, ultimately, as well, synthesize Gasoline from Carbon Dioxide.

And, intriguingly, note, that, in our reproduction of the Abstract from "USP 5,720,858", our United States Government's process for converting Methane into Methanol, also, as in "methanol and hydrogen", produces Hydrogen as a by-product of the Methanol synthesis.

We submit that such by-product Hydrogen could then be employed, as seen in:

WVU Hydrogenates Coal Tar | Research & Development; concerning: "Hydrogenation of Naphthalene and Coal Tar Distillate; West Virginia University; 2009; The hydrogenation of ... coal-tar distillates ... in the presence of hydrogen ... (to obtain) ... the hydrogenated product, tetralin"; which can then serve in WVU's "West Virginia Process" for the direct liquefaction of Coal, to help effect, as WVU puts it: "the conversion of coal to refinable crude hydrocarbons, from which liquid fuels such as gasoline, diesel, kerosene, etc., can be produced";

to help convert some of our abundant Coal into liquid hydrocarbon fuels, as part a combined process that starts with the "solar conversion of carbon dioxide and water vapor to methane", followed by another that, using, essentially, Solar energy, converts "methane to ... methanol and hydrogen", followed by others that convert the Methanol to Gasoline and use the by-product Hydrogen to convert Coal into "gasoline, diesel (and) kerosene".