WV Coal Member Meeting 2024 1240x200 1 1

Exxon CO2 and Methane to Syngas via Microwave Radiation

United States Patent: 5266175

We have, once or twice over the long course of our reportage, touched on yet another way in which various Carbon resources, including Coal and CO2, and co-reactants such as H2O, can be broken down into their more basic elemental and molecular constituents, so that a blend of those constituents, a "synthesis gas", can be formed; which synthesis gas can then be catalytically reacted and reconstituted into hydrocarbon compounds.

Most often, heat energy derived from the partial oxidation of Coal is utilized to drive those processes of decomposition which form the syngas; although, as we've reported, various of our USDOE National Laboratories have developed technologies that rely on heat energy derived from nuclear reactors, solar radiation and hydro-electric power to the same end.

 

 

Such technologies would actually help both to conserve our Coal, in the larger sense, by conserving the latent chemical energy in the reactants being processed into hydrocarbons; and, to conserve the total amount of energy that would need to be applied to such processes by minimizing the co-production of unwanted by-products of oxidation, such as Carbon Dioxide, which would then require additional energy inputs to be dealt with, one way or the other.

As it happens, electricity, derived preferably, in our point of view and again to conserve our precious Coal, from environmental sources, can be used in a fashion different from straightforward electrical resistance heating to accomplish the breakdown, or, preferably, the chemical "activation" of Carbon resources.

As seen, for just two examples out of several, in our reports of:

Idaho Recycles CO2 | Research & Development; concerning: "Syntrolysis: Simultaneously electrolyzing water and carbon-dioxide into Syngas"; and, the related:

USDOE Converts Coal, CO2 and H2O to Hydrocarbon Syngas | Research & Development; concerning: "United States Patent Application 20090235587 - Methods and Systems for Producing Syngas; 2009; Assignee: Battelle Energy Alliance, Idaho Falls (i.e., the USDOE's Idaho National Laboratory) Abstract: Methods and systems are provided for producing syngas utilizing heat from thermochemical conversion of a carbonaceous fuel to support decomposition of at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells";

ways are being, and have been, developed to "leverage" available electrical energy, and to make it's use in Carbon conversion, especially and specifically CO2-recycling, processes more efficient.

Other innovative ways of maximizing the utility of electricity in such processes include first converting that electricity into other forms of energy which are more easily and more efficiently conveyed into the blend of chemical reactants.

Although some of our earlier reports concerning those potentials seem to have slipped through the cracks, perhaps during one of our major computer meltdowns, we remind of one of them still accessible on the West Virginia Coal Association's web site, via:

Switzerland Recycles CO2 to Fuel | Research & Development; concerning the: "Hydrogenation of Carbon Dioxide to Methanol with a Discharge-Activated Catalyst; ABB Corporate Research Ltd.; Abstract: To mitigate greenhouse gas CO2 emissions and recycle its carbon source, one possible approach would be to separate CO2 from the flue gases of power plants and to convert it to a liquid fuel, e.g., methanol. Hydrogenation of CO2 to methanol is investigated in a dielectric-barrier discharge (DBD) with and without the presence of a catalyst. Comparison of experiments shows that this nonequilibrium discharge can effectively lower the temperature range of optimum catalyst performance."

We intended to, prior to our technical disruptions, follow up with further expositions of the ABB technology; and we will, in the future, certainly do so.

However, the exotic-sounding "dielectric-barrier discharge", referred to above, is actually a phenomenon many might already be familiar with, especially those who have attempted to reheat food in a microwave oven without first removing the aluminum foil in which that food might have been wrapped.

The resulting sparks and crackles were "dielectric barrier discharge"s; and, they represent what is sometimes referred to as a "non-thermal" source of energy which can be targeted, as in the Swiss ABB Corporation technology cited above, on driving chemical reactions, especially Carbon conversion reactions.

Somewhat unsurprisingly, as innovative as the USDOE's "Syntrolysis" and ABB's "Discharge-Activated" processes might at first sound, they are only trailing the Size 12 hoof prints already left by Big Oil.

We've previously made report of the Oil industry's earlier development of Carbon Dioxide recycling technology somewhat similar in concept to our USDOE's "Syntrolysis", as seen via:

Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development; concerning: "United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes; 1987; Assignee: The Standard Oil Company; Abstract: A process for the electrocatalytic reduction of carbon dioxide comprises immersing a transition metal complex with square planar geometry into an aqueous or nonaqueous solution (of) carbon dioxide, applying an electrical potential ... and reducing the carbon dioxide to carbon monoxide."

And, herein, we see that the Oil industry has, as well, already trampled the somewhat technically-different path the Swiss ABB scientists now seem to be hiking.

Comment, concerning where we get the Methane, follows excerpts from the initial link in this dispatch to:

"United States Patent 5,266,175 - Conversion of Methane, CO2 and H2O Using Microwave Radiation

Date: November, 1993

Inventor: William Murphy, CA

Assignee: Exxon Research and Engineering Company, NJ

Abstract: A mixture of methane, water and carbon dioxide can be effectively converted to carbon monoxide and hydrogen by subjecting the mixture to microwave radiation in the presence of at least one plasma initiator that is capable of initiating an electric discharge in an electromagnetic field.

(We'll interrupt right here to remind you, lest there be any doubts, that, as seen our report of:

British Petroleum Coal Syngas to Motor Fuels | Research & Development; concerning: "United States Patent Application 20090298958 - Fischer Tropsch Process; 2009; Assignee: BP Exploration Operating Company Limited; Abstract: The present invention relates to a process for converting synthesis gas to hydrocarbons, in particular to hydrocarbons in the C5-C60 range particularly suitable for use as liquid motor fuels", wherein it is stated to be "well known that synthesis gas, i.e., hydrogen and carbon oxide(s), can be converted to hydrocarbons"; that:

"synthesis gas" does, indeed, consist of "hydrogen and carbon oxide(s)", i,e,, Exxon's "carbon monoxide and hydrogen"; and, it can, most certainly, "be converted to hydrocarbons" that are "particularly suitable for use as liquid motor fuels".)

Claims: A method for converting methane and carbon dioxide to carbon monoxide and hydrogen which comprises: 

(a) introducing a feed stream containing methane, carbon dioxide and ... water ... into a reaction zone that contains at least one plasma initiator which initiates an electric discharge in an electromagnetic field, 

(b) subjecting the reaction zone to microwave radiation thereby initiating an electric discharge in said reaction zone, and 

(c) ionizing the methane, carbon dioxide and water reactants whereby at least a portion of the methane and carbon dioxide are converted to carbon monoxide and hydrogen.

Summary: This invention relates to a method for converting methane and carbon dioxide in the presence of water to carbon monoxide and hydrogen using microwave radiation."

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We'll cut our excerpts from Exxon's CO2-recycling "United States Patent 5,266,175" relatively short, since their process for efficiently converting Carbon Dioxide into "carbon monoxide and hydrogen" hydrocarbon synthesis gas does require, in addition to Water, that Methane be included in the reaction mix.

And, we remind you, that, as documented in:

Texaco Clean Methane from High-Sulfur Coal | Research & Development; which concerns: "United States Patent 3,928,000 - Clean Methane ... from High-Sulfur Containing Hydrocarbonaceous Materials; 1975; Assignee: Texaco Incorporated; Abstract: This is an improved process for converting low-cost high-sulfur containing hydrocarbonaceous materials into a clean methane-rich gas stream"; and, in:

Chicago Recycles CO2 to Methane | Research & Development; which makes exposition of: "United States Patent 4,609,440 - Electrochemical Synthesis of Methane; 1986; Assignee: Gas Research Institute, Chicago; Abstract: A method is described for electrochemically reducing carbon dioxide to form methane";

we can make all the Methane we might want, for use in Exxon's efficient Carbon Dioxide-recycling process of "United States Patent 5,266,175", out of some of our abundant Coal, or, even more Carbon Dioxide.

That should, and likely, when it's posted, will, neatly tie-up and conclude our presentation of USP 5,266,175, and enable the easy excision of our concluding comments, which are:

Ain't it far past time some of us went out to the cemetery, dug up what remains of old John L. Lewis, ground up his bones, and then slipped some of the powder into the soy milk and herbal tea our Coal Country journalists and elected representatives seem to have lately taken to drinking?

Maybe then their blood would get thicker, they might grow some hair on their chests and their knuckles, and they wouldn't be so compelled to draw the curtains and dim the lights when the CO2-rustling cowboys from Texas stampeded at night through the back yard.

As we have attempted to document for everyone in multiple reports, the Texas oil industry knows all about the fact that Carbon Dioxide can be productively recycled, as herein, into hydrocarbon fuels.

We insist that is why they are so fired up about the prospect of mandated Carbon Dioxide sequestration in nearly-depleted natural petroleum reservoirs; and, with the cooperation of Texas-area governmental entities, have established organizations which promote the Geologic Sequestration of Carbon Dioxide, such as the:

Gulf Coast Carbon Center: wherein we're treated to self-serving blather like:

"Carbon Dioxide Sequestration in Geologic Media; Burning fossil fuel (gas, oil, and coal) has measurably increased the total load of carbon dioxide in the atmosphere.

Although the long-term consequences of these changes are hotly debated, one likely outcome is the alteration of global climate as greenhouse gases trap heat at the earth's surface. One possible response is capture gasses after combustion and reinject them into subsurface settings where they will be retained for geological periods of time.

The GCCC seeks to apply its technical and educational resources to implement geologic storage of anthropogenic carbon dioxide on an aggressive time scale with a focus in a region where large-scale reduction of atmospheric releases is needed and short term action is possible."